
If you paint a monochramatic gray underpainting and colorize it by simply multiplying it by a base color, you'll get a dull image. Even if you hand pick and paint every color in your image, if you rely only on the luminosity slider, you'll have the same problems. You see this luminosity slider reliance a lot, especially in the skin tones of the work of beginning painters.
When a form turns away from light it usually experiences a hue shift. This often happens simply because the fill light is a different color from the key light. Regardless of why it happens, however, it usually looks better when it happens. So when you paint or light 3D, identify or invent a reason to shift the hue warmer or cooler, and sell it.
Here's a related link:
Avoiding Ugly Color Falloff in 3D

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