Relative Color & Value:
To approach naturalistic color and value, one must accept relative color and value. That is to say, to convincingly illustrate what one sees, one must provide clues to the context in which something is seen.

The same shade of orange appears in each square.
This illustrates how three colors may appear to be four.
Something that is dark, light, red, or blue appears that way relative to its surroundings. Imagine a person wearing a blue shirt, standing in the desert, compared to the same person swimming in the sea.
Colors interact with one-another. If a color appears cool (leaning towards blue-green), it may be due to neighboring warm colors (red-yellow). (And vice versa.)
Reducing color to warms and cools helps to keep relativity in mind. In painting, inaccurate color is usually attributed to inaccurate sight, rather than clumsy color mixing. Painting with a limited palette helps to train the eye to see warms and cools, instead of specific colors.
I often begin paintings with a limited palette of Burnt Sienna, Ivory Black, and Titanium White.
Sienna and Black, mixed together, produce a neutral dark (which mixes with White to produce a neutral gray).
Sienna and White, mixed together, produce a warm, rusty-orange.
Ivory Black, mixed with White, produces a cool gray, which leans toward blue. (Ultramarine Blue, can replace Ivory Black, if a cooler result is desired. Blue mixes with Sienna to produce a similarly neutral dark.)
I find, when working with this palette, that it is helpful never to use a pure color. Instead, a mixture of Sienna & Black is pushed warmer or cooler with more, or less of the other.
Value operates the same way. If something appears light, it may be due to dark surroundings.

The center rectangle is one solid shade of gray.
(09/22/08)