@kjetil b halvorsen gives a nice discussion of the geometric intuition behind positive semi-definiteness as a partial ordering. I'll give a more grubby-handed take on that same intuition. One which proceeds from what sorts of calculations you might like to do with your variance matrixes.
Suppose you have two random variables $x$ and $y$. If they are scalars, then we can calculate their variances as scalars, and compare them in the obvious way using the scalar real numbers $V(x)$ and $V(y)$. So if $V(x)=5$ and $V(y)=15$, we say that the random variable $x$ has a smaller variance than does $y$.
On the other hand, if $x$ and $y$ are vector-valued random variables (let's say they are two-vectors), how we compare their variances is not so obvious. Say their variances are:
\begin{align}
V(x) = \left[ \begin{array}{c c} 1 & 0.5 \\ 0.5 & 1 \end{array} \right] \qquad
V(y) = \left[ \begin{array}{c c} 8 & 3 \\ 3 & 6 \end{array} \right]
\end{align}
How do we compare the variances of these two random vectors? One thing we could do is just compare the variances of their respective elements. So, we can say that the variance of $x_1$ is smaller than the variance of $y_1$ by just comparing real numbers, like: $V(x_1)=1<8=V(y_1)$ and $V(x_2)=1<6=V(y_2)$. So, maybe we could say that the variance of $x$ is $\le$ the variance of $y$ if the variance of each element of $x$ is $\le$ the variance of the corresponding element of $y$. This would be like saying $V(x) \le V(y)$ if each of the diagonal elements of $V(x)$ is $\le$ the corresponding diagonal element of $V(y)$.
This definition seems reasonable at first blush. Furthermore, as long as the variance matrixes we are considering are diagonal (i.e. all covariances are 0), it is the same as using semi-definiteness. That is, if the variances look like
\begin{align}
V(x) = \left[ \begin{array}{c c} V(x_1) & 0 \\ 0 & V(x_2) \end{array} \right] \qquad
V(y) = \left[ \begin{array}{c c} V(y_1) & 0 \\ 0 & V(y_2) \end{array} \right]
\end{align}
then saying $V(y)-V(x)$ is positive-semi-definite (i.e. that $V(x) \le V(y)$) is just the same as saying $V(x_1) \le V(y_1)$ and $V(x_2) \le V(y_2)$. All seems good until we introduce covariances. Consider this example:
\begin{align}
V(x) = \left[ \begin{array}{c c} 1 & 0.1 \\ 0.1 & 1 \end{array} \right] \qquad
V(y) = \left[ \begin{array}{c c} 1 & 0 \\ 0 & 1 \end{array} \right]
\end{align}
Now, using a comparison which only considers the diagonals, we would say $V(x) \le V(y)$, and, indeed, it's still true that element-by-element $V(x_k) \le V(y_k)$. What might start to bother us about this is that if we calculate some weighted sum of the elements of the vectors, like $3x_1 + 2x_2$ and $3y_1 + 2y_2$, then we run into the fact that $V(3x_1 + 2x_2) \gt V(3y_1 + 2y_2)$ even though we are saying $V(x) \le V(y)$.
This is weird, right? When $x$ and $y$ are scalars, then $V(x) \le V(y)$ guarantees that for any fixed, non-random $a$, $V(ax) \le V(ay)$.
If, for whatever reason, we are interested in linear combinations of the elements of the random variables like this, then we might want to strengthen our definition of $\le$ for variance matrixes. Maybe we want to say $V(x) \le V(y)$ if and only if it is true that $V(a_1x_1 + a_2x_2) \le V(a_1y_1 + a_2y_2)$, no matter what fixed numbers $a_1$ and $a_2$ we pick. Notice, this is a stronger definition than the diagonals-only definition since if we pick $a_1=1,a_2=0$ it says $V(x_1) \le V(y_1)$, and if we pick $a_1=0,a_2=1$ it says $V(x_2) \le V(y_2)$.
This second definition, the one which says $V(x) \le V(y)$ if and only if $V(a'x) \le V(a'y)$ for every possible fixed vector $a$, is the usual method of comparing variance matrixes based on positive semi-definiteness:
\begin{align}
V(a'y) - V(a'x) = a'V(x)a - a'V(y)a = a'\left(V(x) - V(y) \right)a
\end{align}
Look at the last expression and the definition of positive semi-definite to see that the definition of $\le$ for variance matrixes is chosen exactly to guarantee that $V(x) \le V(y)$ if and only if $V(a'x) \le V(a'y)$ for any choice of $a$, i.e. when $\left( V(y)-V(x) \right)$ is positive semi-definite.
So, the answer to your question is that people say a variance matrix $V$ is smaller than a variance matrix $W$ if $W-V$ is positive semi-definite because they are interested in comparing the variances of linear combinations of the elements of the underlying random vectors. What definition you choose follows what you are interested in calculating and how that definition helps you with those calculations.
a
andb
, ifa-b
is positive then we would say that upon removing variabilityb
out ofa
there remains some "real" variability left ina
. Likewise is a case of multivariate variances (= covariance matrices)A
andB
. IfA-B
is positive definite then that means thatA-B
configuration of vectors is "real" in euclidean space: in other words, upon removingB
fromA
, the latter is still a viable variability. $\endgroup$