The Law of Cosines gives:
$$a^2 = b^2 + c^2 - 2bc \cos(A)$$
$$b^2 = a^2 + c^2 - 2ac \cos(B)$$
$$c^2 = a^2 + b^2 - 2ab \cos(C)$$
Adding these three equations gives:
But $A = \pi - (B + C)$, so
$$\cos(A) = \cos(\pi - (B + C))$$
$$= \cos(\pi)\cos(B + C) + \sin(\pi)\sin(B + C)$$
$$= -\cos(B + C)$$
$$= -(\cos(B)\cos(C) - \sin(B)\sin(C))$$
$$= (\sin(B)\sin(C) - \cos(B)\cos(C)$$
We are given that $\cos(C) = -\sin(B)$. Since $\sin^2(C) = 1 - \cos^2(C) = 1 - \sin^2(B) = \cos^2(B)$, we have $\sin(B) = \pm \cos(B)$. So,
$$a^2 = b^2 + c^2 - 2bc (\pm \cos(B)\sin(B) + \cos(B)\sin(B))$$
$$b^2 = a^2 + c^2 - 2ac \cos(B)$$
$$c^2 = a^2 + b^2 + 2ab \sin(B)$$
If we chose $\sin(C) = -\cos(B)$, then $\triangle ABC$ is a right triangle with A being the right angle. We have $a^2 = b^2 + c^2$, So $\frac{a^2 + b^2}{c^2} = \frac{2b^2 + c^2}{c^2} = 2\frac{b^2}{c^2} + 1$. This approaches a minimum value of 1 when $b$ is as small as possible relative to $c$.
For the rest of this answer, I'll examine the case when $\sin(C) = +\cos(B)$. Then the first equation above simplifies to $a^2 = b^2 + c^2 - 4bc \cos(B)\sin(B)$.
From the last two equations above, we get $\cos(B) = \frac{a^2 + c^2 - b^2}{2ac}$ and $\sin(B) = \frac{c^2 - a^2 - b^2}{2ab}$. Thus,
$$a^2 = b^2 + c^2 - 4bc (\frac{a^2 + c^2 - b^2}{2ac}) (\frac{c^2 - a^2 - b^2}{2ab})$$
Multiplying through by $(2ac)(2ab) = 4a^2bc$ to get rid of the fractions gives:
$$4a^4bc = 4a^2b^3c + 4a^2bc^3 - 4bc (a^2 + c^2 - b^2) (c^2 - a^2 - b^2)$$
$$a^4 = a^2b^2 + a^2c^2 - (a^2 + c^2 - b^2) (c^2 - a^2 - b^2)$$
$$a^4 = a^2b^2 + a^2c^2 - (a^2c^2 - a^4 - a^2b^2 + c^4 - a^2c^2 - b^2c^2 - b^2c^2 + a^2b^2 + b^4)$$
$$a^4 = a^2b^2 + a^2c^2 - a^2c^2 + a^4 + a^2b^2 - c^4 + a^2c^2 + b^2c^2 + b^2c^2 - a^2b^2 - b^4$$
$$b^4 - 2b^2c^2 + c^4 = a^2(b^2 + c^2)$$
$$a^2 = \frac{(b^2 - c^2)^2}{b^2 + c^2}$$
Plugging this into the target expression gives:
$$q := \frac{a^2 + b^2}{c^2}$$
$$= \frac{\frac{(b^2 - c^2)^2}{b^2 + c^2} + b^2}{c^2}$$
$$= \frac{(b^2 - c^2)^2 + b^2(b^2 + c^2)}{c^2(b^2 + c^2)}$$
$$= \frac{2b^4 + c^4 - b^2c^2}{c^2(b^2 + c^2)}$$
Let $b = cx$. Then
$$q = \frac{2c^4x^4 + c^4 - c^4x^2}{c^2(c^2x^2 + c^2)}$$
$$= \frac{2c^4x^4 - c^4x^2 + c^4}{c^4x^2 + c^4}$$
$$= \frac{2x^4 - x^2 + 1}{x^2 + 1}$$
Let $u = x^2$. Then:
$$q = \frac{2u^2 - u + 1}{u + 1}$$
Setting the derivative equal to zero gives:
$$\frac{dq}{du} = \frac{(4u - 1)(u + 1) - (2u^2 - u + 1)(1)}{(u + 1)^2} = 0$$
$$(4u - 1)(u + 1) - (2u^2 - u + 1) = 0$$
$$4u^2 + 3u - 1 - 2u^2 + u - 1 = 0$$
$$2u^2 + 4u - 2 = 0$$
$$u^2 + 2u - 1 = 0$$
$$u = \frac{-2 \pm \sqrt{8}}{2}$$
$$u = -1 \pm \sqrt{2}$$
But since triangles can't have negative or imaginary side lengths, only the positive root makes sense. So $u = \sqrt{2} - 1$. Thus:
$$q = \frac{2(\sqrt{2} - 1)^2 - (\sqrt{2} - 1) + 1}{(\sqrt{2} - 1) + 1}$$
$$= \frac{2(2 - 2\sqrt{2} + 1) - \sqrt{2} + 1 + 1}{\sqrt{2}}$$
$$= \frac{8 - 5\sqrt{2}}{\sqrt{2}}$$
$$= \frac{8}{\sqrt 2} - 5$$
$$= 4 \sqrt 2 - 5$$
So, my solution agrees with your Solution 2.