mtl_sky(.emissive_...) affects the color of the sky only when red,green,blue is lower than 255. And the opposite way, red,green,blue only make changes when mtl_sky.emissive_... is lower than 255.
So it seems the light formular is simply mtl_sky.emissive_...+[sky].red/green/blue, with the maximum of 255 for sure.
The only (fast) way I see to make the sky completly white is to use a shader. Making a another sky layer is very framerate unfriendly.