In addition to the algebraic reason that Robert Israel gave, there's a very nice "moral reason" that the Kullback-Leibler divergence is not symmetric. Roughly speaking, it's because you should think of the two arguments of the KL divergence as different kinds of things: the first argument is empirical data, and the second argument is a model you're comparing the data to. Here's how it works.
Take a bunch of independent random variables $X_1, \ldots, X_n$ whose possible values lie in a finite set.* Say these variables are identically distributed, with $\operatorname{Pr}(X_i = x) = p_x$. Let $F_{n,x}$ be the number of variables whose values are equal to $x$. The list $F_n$ is a random variable, often called the "empirical frequency distribution" of the $X_i$. What does $F_n$ look like when $n$ is very large?
More specifically, let's try to estimate the probabilities of the possible values of $F_n$. Since the set of possible values is different for different $n$, take a sequence of frequency distributions $f_1, f_2, f_3, \ldots$ approaching a fixed frequency distribution $f$. It turns out** that
$$\lim_{n \to \infty} \tfrac{1}{n} \ln \operatorname{Pr}(F_n = f_n) = -\operatorname{KL}(f, p).$$
In other words, the Kullback-Leibler divergence of $f$ from $p$ lets you estimate the probability of getting an empirical frequency distribution close to $f$ from a large number of independent random variables with distribution $p$.
You can find everything I just said, and more, in the excellent article "Information Theory, Relative Entropy and Statistics," by François Bavaud.
* You can also do this more generally, but I don't know anything about that.
** Using Stirling's approximation, $\ln k! \in k\ln k - k + O(\ln k)$.