Note that
$$
\sqrt{\left(p - \frac14\right)^2 + \left(q - \frac14\right)^2 + \left(r - \frac14\right)^2 + \left(s - \frac14\right)^2}
$$
is the Euclidean distance from $\left(\frac14,\frac14,\frac14,\frac14\right)$ to $(p, q, r, s)$. Thus the question here is, which point $(p, q, r, s)$ with the given restraints $p + q + r + s = 1$ and $p, q, r, s\geq 0$ (which gives a regular tetrahedron) is the furthest away from $\left(\frac14,\frac14,\frac14,\frac14\right)$ (which is the center of the tetrahedron)? Geometric intuition says that this happens in the corners, which is to say one variable equal to $1$, the rest equal to $0$. The corresponding maximal value is
$$
\frac9{16} + 3\cdot \frac1{16} = \frac{3}{4}
$$
This also hints that Lagrange multipliers wouldn't really work, as there is no maximum on the hyperplane $p + q + r + s = 1$ that the multipliers can find. Thus the maximum must occurr on the boundary of the region of that hyperplane, given by setting one of $p, q, r, s$ to $0$. But even then, the maximum occurrs in the corners, where the constraints aren't differentiable, and the Lagrange multiplier method fails.
That being said, finding the minimum $(p, q, r, s) = (\frac14,\frac14,\frac14,\frac14)$ is very doable with Lagrange multipliers, although in that case Magrange multipliesr may be a bit overkill as the solution is plainly visible.