Alternative proof:
It suffices to prove that, for $x > 0$,
$$\sqrt{1 - \mathrm{e}^{-4x^2/\pi}} - \frac{2}{\sqrt{\pi}}\int_0^x \mathrm{e}^{-t^2} \mathrm{d} t \ge 0.$$
Denote LHS by $f(x)$. We have
$$f'(x) = \frac{4x \mathrm{e}^{-4x^2/\pi}}{\pi\sqrt{1 - \mathrm{e}^{-4x^2/\pi}}}
- \frac{2}{\sqrt{\pi}}\mathrm{e}^{-x^2}.$$
Fact 1: $f'(x) = 0$ has exactly one positive real solution, denoted by $x_0$.
(The proof is given at the end.)
By Fact 1 and $f'(1) > 0$ and $f'(2) < 0$, we have $f'(x) > 0$ on $(0, x_0)$ and $f'(x) < 0$ on $(x_0, \infty)$.
Thus, $f(x)$ is strictly increasing on $(0, x_0)$ and strictly decreasing on $(x_0, \infty)$.
Also, $f(0) = 0, f(\infty) = 0$. Thus, $f(x) > 0$ on $(0, \infty)$. We are done.
Proof of Fact 1:
For $x > 0$, we have
\begin{align}
f'(x) = 0 \quad &\Longleftrightarrow \quad
\left(\frac{4x \mathrm{e}^{-4x^2/\pi}}{\pi\sqrt{1 - \mathrm{e}^{-4x^2/\pi}}}\right)^2
= \left(\frac{2}{\sqrt{\pi}}\mathrm{e}^{-x^2}\right)^2\\[6pt]
\quad &\Longleftrightarrow \quad \frac{4x^2}{\pi} = \mathrm{e}^{8x^2/\pi} \mathrm{e}^{-2x^2}(1 - \mathrm{e}^{-4x^2/\pi})
\\[6pt]
\quad &\Longleftrightarrow \quad
\frac{4x^2}{\pi} + \mathrm{e}^{(1-\pi/2)\cdot \frac{4x^2}{\pi}} = \mathrm{e}^{(2-\pi/2)\cdot \frac{4x^2}{\pi}}\\
&\Longleftrightarrow \quad u + \mathrm{e}^{(1-\pi/2)u} = \mathrm{e}^{(2-\pi/2)u}, \quad u = \frac{4x^2}{\pi}.
\end{align}
Let $g(u) = u + \mathrm{e}^{(1-\pi/2)u} - \mathrm{e}^{(2-\pi/2)u}$. We have
$$g'(u) = 1 + (1-\pi/2)\mathrm{e}^{(1-\pi/2)u} - (2-\pi/2)\mathrm{e}^{(2-\pi/2)u}$$
and $$g''(u) = (1-\pi/2)^2\mathrm{e}^{(1-\pi/2)u} - (2-\pi/2)^2\mathrm{e}^{(2-\pi/2)u}.$$
Let $u_0 = 2\ln (\pi - 2) - 2\ln (4 - \pi)$.
It is easy to prove that $g''(u) > 0$ on $(0, u_0)$, and $g''(u) < 0$ on $(u_0, \infty)$.
Thus, $g'(u)$ is strictly increasing on $(0, u_0)$, and strictly decreasing on $(u_0, \infty)$.
Also, $g'(0) = 0$ and $g'(\infty) = -\infty$. Thus, $g'(u) = 0$ has exactly one positive real solution, denoted by $u_1$.
Thus, $g'(u) > 0$ on $(0, u_1)$, and $g'(u) < 0$ on $(u_1, \infty)$.
Thus, $g(u)$ is strictly increasing on $(0, u_1)$, and strictly decreasing on $(u_1, \infty)$.
Also, $g(0) = 0$ and $g(\infty) = -\infty$. Thus, $g(u) = 0$ has exactly one positive real solution.
As a result, $f'(x) = 0$ has exactly one positive real solution. We are done.
$x=0$
also tells us why$k=4/\pi$
is the best possible. But I don't know if there is a simple proof of the inequality. Would love to see one. $\endgroup$