Use absolutely convergent sum definitions for $e$ and $\pi$:
$$e^x=1+\sum_{n=1}^\infty{x^n \over n!}$$
and
$${\pi^2 \over 6} = \sum_{n=1}^\infty{1 \over n^2}$$
Then assume $e \ge \pi$, so $e^2 \ge \pi^2$, which means
$$1+\sum_{n=1}^\infty{2^n \over n!} \ge 6\sum_{n=1}^\infty{1 \over n^2}$$
$$\iff 1+\sum_{n=1}^\infty{{2^n\over n!}-{1\over n^2}} \ge 5\sum_{n=1}^\infty{1 \over n^2}$$
For all $n \ge 8$, ${2^n \over n!} \lt {1\over n^2}$, so $\sum_{n=8}^\infty{{2^n\over n!}-{1\over n^2}} \lt 0$. This means that
$$1+\sum_{n=1}^7{{2^n \over n!}-{1\over n^2}} \gt 5\sum_{n=1}^\infty{1\over n^2}$$
or more simply,
$$1+\sum_{n=1}^7{2^n \over n!} \gt 5\sum_{n=1}^\infty{1\over n^2}$$
$$\iff 1+2/1+4/2+8/6+16/24+32/120+64/720+128/5040 \gt 5+5/4+5/9+5/16+5/25+5/36+5/49+...$$
$$\iff 1/4+1/9+1/15+4/45+8/315 \gt 5/16+5/36+5/64+5/49+5/81+...$$
Which is clearly impossible given that paired LHS and RHS terms are all such that (LHS term) $\lt$ (RHS term), and that the LHS has only the terms shown. Therefore, our initial assumption is false, meaning that $e\lt\pi$.
It is difficult to say what can be learned from this. I think the clearest comparison would be if there were a definite limit statement for the value of $\pi$, rather than a geometric one, for which there is no "natural" geometric equivalent for $e$. Nevertheless, this sum comparison at least shows the difference between $\dfrac {2^n}{n!}$ and $\dfrac {1}{n^2}$.