Ant--
Chris is right.
We think that some colors, such as uniform and flag colors are a fixed and immutable hue, value or saturation. But our perception of colors and their subsequent rendering will always be influenced by the color of the light falling on them.
The way to color harmony and balance is first to determine the temperature of the light--first whether the light is warm or cool, and if possible, if the light has a particular cast or hue, like the warm yellow-orange of sunrise or sunset, for example. In a certain color light, all colors the same temperature (and hue) of the light will be more saturated, and all the complementary colors will be grayed back and less saturated. Not all colors in a scene will have equal saturation.
Also, as a rule, cool light sources will have warm shadows, and warm light sources will have cool shadows, unless the light is peculiarly artificial such as stage lighting, for instance, and maybe even then.
There is a place for more grayed back, neutral colors and highly saturated ones in the same painting, the same as in nature. Again, for me, the key to figuring out what to use where hinges on determining the temperature of the light, and committing to it throughout.
Or as Richard Schmidt counsels, don't ask "What color goes with what?" like an interior decorator would, but "What is or isn't possible under this light."
Best--TE
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