Let $$ \cos^{-1}x=a \implies x=\cos a $$ and $$ \cos^{-1}(-x)=b \implies -x=\cos b $$ Hence we have $$ \cos a+\cos b=0 $$ Using $$ \cos(A+B)+\cos(A-B)=2\cos A\cos B $$ with $$ A=\frac{a+b}{2} \\ \text{ and } \\ B=\frac{a-b}{2} $$ we get $$ \cos a+\cos b=2\cos\left(\frac{a+b}{2}\right) \cos\left(\frac{a-b}{2}\right)=0 $$ with which $$ \cos\left(\frac{a+b}{2}\right)=0 \text{ or } \cos\left(\frac{a-b}{2}\right)=0\\ \implies a=\pi-b \text{ or } a=\pi+b $$
Now, to choose between the two, I'm making the below argument:
To find the inverse of a function, the function has to be one-to-one. Hence in our case, both $\cos a$ and $\cos b$ have to be one-to-one, which is possible only when
$$
n\pi\leq a,b \leq (n+1)\pi \text{, }n\in\mathbb{Z}
$$
From the above, we get, $$ -n\pi \leq \pi-b \leq (-n+1)\pi $$ and $$ (n+1)\pi \leq \pi+b \leq (n+2)\pi $$
The ranges can be reconciled for $a$ and $\pi-b$ by taking $n=0$ and we get $$ 0 \leq a \leq \pi \\ 0 \leq \pi-b \leq \pi $$
But no value of $n\in\mathbb{Z}$ can simultaneously reconcile the ranges of $a$ and $\pi+b$.
Therefore, we conclude that $$ \cos^{-1}(-x)=\pi-\cos^{-1}(x) $$
From this I also learnt that the inverse function is meaningful when the angle is discussed in the range $[0,\pi]$. Is this line of argument mathematically fool-proof?