Color has three components: value, hue, and saturation. Of these three, value is the most important one. Jiggle left-and-right from the color harmony of your choice, as long as values are not messed up. Color loves change. So slight saturation and hues variations are good things.
No, no. Use any color you want, but keep overall color logic consistent. F.e. far objects are less saturated, shadows are colder/warmer etc. (maintaining good value structure is the main logic)
If values are organized, it will never collapse. Also, keep in mind that the color harmony of the picture can be different from the character's color harmony from the character sheet.