All right! In my opinion, it's meaningful to look at the symmetry of discrete random variables. As to how to characterize the symmetry of a discrete random variable, I think that for an multinomial random variable, firstly the values it takes must be symmetric about one point and then the corresponding probabilities are equal. Like for instance,
random variable $X=\{1,2,\cdots,c\}$, and $P\{X=i\}=P\{X=c+1-i\}$ for all $i=1,2,\cdots,c$.
For other kinds of distributions, such as binomial distribution $B(n,p)$, I suppose that it's a symmetric distribution only if $p=\frac{1}{2}$. Actually, it's just my idea, maybe it's wrong. Hope others tell me their ideas.