Let's clarify some of the issues.
Convexity
Consider a real-valued function function $f$ defined on an interval $I$ of real numbers. (Everything that follows extends naturally and obviously to functions defined on sets $I\subset \mathbb{R}^d$ provided $I$ is a convex set, but I won't belabor that point. The key property enjoyed by $I$ is that "mixtures" of elements of $I$ are in $I;$ this will be elaborated below.)
$f$ has a graph (the set of points $(x,f(x))$ where $x\in I$). The convexity of $f$ (in the sense given in the question) is equivalent to the graph always "curving upwards." This concept can be made rigorous in various ways; one nice one is that all points on any line segment connecting any two points on the graph of $f$ lie on or above the graph. This is just a geometric restatement of convexity.
One consequence of convexity is this: given any finite number $n$ of points $x_i,$ $i=1,2,\ldots, n$ in $I$ and any set of non-negative numbers ("weights") $w_i$ summing to unity, $$\sum_{i=1}^n w_i\,f(x_i) \ge f\left(\sum_{i=1}^n w_i\,x_i\right).\tag{1}$$
(The right hand side is defined because the conditions on the $w_i$ imply the argument of $f$ lies inside $I,$ allowing us to apply $f$ to it. For brevity, let's call linear combinations where the coefficients are non-negative and sum to unity "mixtures" of the values.)
This figure illustrates the idea of the following proof in the case $n=3:$
The convexity of $f$ is equivalent to all line segments of points on its graph lying within the shaded region on or above its graph (the "epigraph" of $f$). (That is, the epigraph is a convex region.) Points on line segments are mixtures of their endpoints. Mixtures involving $n\gt 2$ points can be considered mixtures of mixtures, making it obvious that they, too, lie in the epigraph. In this figure, the weights are represented by the areas of point symbols.
Proof: Use induction on $n,$ beginning with the "base case" $n=2,$ which is just the defining property of $f.$ Assume hypothetically that $(1)$ holds for a given $n\ge 2$ and all applicable $x_i$ and $w_i.$ Let $x_i$ and $w_i,$ $i=1,2,\ldots, n+1,$ be $n+1$ points in $I$ with $n+1$ weights, respectively. If the last weight $w_{n+1}$ is zero then (1) applies immediately to the other $n$ points. It remains to treat the case where $w_{n+1}\ne 0.$ This enables us to focus on the first $n$ weights and renormalize them to sum to unity upon division by $1-w_{n+1}:$
$$\eqalign{
\sum_{i=1}^{n+1} w_i\,f(x_i) &= \sum_{i=1}^{n} w_i\,f(x_i) + w_{n+1}\,f(x_{n+1})\\
&= (1-w_{n+1})\sum_{i=1}^{n} \frac{w_i}{1-w_{n+1}}\,f(x_i) + w_{n+1}\,f(x_{n+1})\\
&\ge (1-w_{n+1})f\left(\sum_{i=1}^{n} \frac{w_i}{1-w_{n+1}}x_i\right) + w_{n+1}\,f(x_{n+1})
}$$
by the inductive hypothesis. But this last expression is a mixture of just two values of $f.$ The convexity of $f$ immediately implies
$$\eqalign{
&(1-w_{n+1})f\left(\sum_{i=1}^{n} \frac{w_i}{1-w_{n+1}}x_i\right) + w_{n+1}\,f(x_{n+1})\\ &\ge f\left(\sum_{i=1}^{n} (1-w_{n+1})\frac{w_i}{1-w_{n+1}}x_i + w_{n+1}\,x_{n+1}\right)\\
&= f\left(\sum_{i=1}^{n+1} w_i\,x_i\right).
}$$
From the assumption that $(1)$ holds for a particular $n\ge 2$ we have deduced $(1)$ also holds for $n+1.$ Thus, $(1)$ holds for all $n\ge 2,$ QED.
Indexing random variables
Recall that a random variable $X$ is function defined on a set of outcomes $\Omega.$ Let $f$ be the function in the question and let $I$ be its domain. For expressions like "$f(X)$" to make sense we must assume the image of $X$ is a subset of $I,$ so that we may define the random variable $f(X)$ to be the function on $\Omega$ given by
$$f(X)(\omega) = f(X(\omega))$$
for all $\omega\in\Omega.$ (This is the composition of the function $f$ with the function $X.$)
Consider $n$ random variables defined on a common set $\Omega.$ Two hundred years ago, expositors would have described them by naming an indefinite sequence of letters, like this: "Let $A,B,C,\ldots, Z$ be a finite collection of random variables." Since then, mathematical terminology has evolved toward using indexing to give such descriptions. An "index" is merely an element of a specified set $S,$ often taken to be $S=\{1,2,\ldots, n\}$ or $S=\{0,1,\ldots, n-1\}.$ Our "$n$ random variables" are then described by supposing we are given a function
$$X: S \to \mathcal{R}(\Omega)\tag{2}$$
where $\mathcal{R}(\Omega)$ is the set of random variables defined on $\Omega.$ When we are indexing and $i\in S$ we don't write $X(i)$ for the random variable associated with $i:$ instead, we write $X_i.$ This is merely a matter of notation; it is not conceptual. Thus,
For each $i\in S,$ $X_i:\Omega\to I$ is a random variable (and these variables are not necessarily distinct).
Often the entire indexed collection of objects is denoted as $(X_i)_{i\in S}.$ This is just another way of writing $(2).$
Convexity applied to random variables
Let $f$ be the function in the question, defined on an interval $I$ and assumed to be convex (and measurable), and let $(X_i)_{i\in S}$ be a finite collection of random variables. Composing $f$ with each $X_i$ produces a random variable $f(X_i):\Omega\to \mathbb{R}.$
Consider any particular outcome $\omega\in\Omega$ and write $x_i = X_i(\omega)$ for each $i\in S.$ We have seen that $f(x_i)=f(X_i(\omega))$ can be considered the value of $f(X_i)$ at $\omega.$ Because $f$ is convex and $x_i\in I,$ for any mixture with coefficients $w_i$ the inequality $(1)$ says
$$\sum_{i\in S} w_i\, f(X_i)(\omega) = \sum_{i\in S} w_i\, f(x_i) \ge f\left(\sum_{i\in S} w_i\,x_i\right) = f\left(\sum_{i\in S} w_i\,X_i(\omega)\right).$$
Take expectations of both sides with respect to the probability measure defined on $\Omega.$ Because expectation respects inequalities (which comes down to the basic and obvious fact that the integral of a non-negative function is a non-negative number), we obtain
$$\mathbb{E}\left[\sum_{i\in S} w_i\, f(X_i)\right] \ge \mathbb{E}\left[f\left(\sum_{i\in S} w_i\,X_i\right)\right].$$
Linearity of expectation lets us re-express the left hand side as
$$\sum_{i\in S} w_i\, \mathbb{E}\left[f(X_i)\right] = \mathbb{E}\left[\sum_{i\in S} w_i\, f(X_i)\right]\ge \mathbb{E}\left[f\left(\sum_{i\in S} w_i\,X_i\right)\right],$$
giving the assertion in the question.