I found the following trick (maybe it's over-complicated ?). I'll let you fill the details.
First, note that the curves of equations $y=\sin^2 (x)$ and $y = 2x/\pi$ have a common central symmetry around $(\pi/4, 1/2)$. In order to take advantage of that, I change coordinates so as to center the integrals on $\pi/4$. Using a few trigonometric formulae (doubling of angle...) and a change of variables,
$$I_1 := \int_0^{\pi/2} e^{-\sin^2 (x)}\text{ d}x = \frac{1}{\sqrt{e}}\int_{-\pi/4}^{\pi/4} e^{-\frac{\sin(2x)}{2}}\text{ d}x,$$
$$I_2 := \int_0^{\pi/2} e^{-\frac{2x}{\pi}}\text{ d}x = \frac{1}{\sqrt{e}}\int_{-\pi/4}^{\pi/4} e^{-\frac{2x}{\pi}}\text{ d}x.$$
Now, $-\frac{\sin(2x)}{2}$ is inferior to $-\frac{2x}{\pi}$ on $(0,\pi/4)$, and superior on $(-\pi/4,0)$. We should expect $I_1$ to be larger than $I_2$ based on this and the fact that most of the mass of the integral comes from $(-\pi/4,0)$, but that needs to be proved, for instance by a convexity argument. Thus the second trick: symmetrize the integrals.
$$I_1 = \int_0^{\pi/2} e^{-\sin^2 (x)}\text{ d}x = \frac{1}{\sqrt{e}}\int_{-\pi/4}^{\pi/4} \cosh \left(\frac{\sin(2x)}{2}\right)\text{ d}x = \frac{2}{\sqrt{e}}\int_0^{\pi/4} \cosh \left(\frac{\sin(2x)}{2}\right)\text{ d}x,$$
$$I_2 = \int_0^{\pi/2} e^{-\frac{2x}{\pi}}\text{ d}x = \frac{2}{\sqrt{e}}\int_0^{\pi/4} \cosh \left(\frac{2x}{\pi}\right) \text{ d}x.$$
The convexity ox the exponential implies that $\cosh$ is convex with a minimum at $0$, and thus increasing on $[0,\pi/4]$. You should be able to conclude from there.