The more I work on miniatures (this is year 17), the more I turn to my original 2D art roots.
This means that I seldom paint the color that "should" be there. When you are painting in oils or watercolors, you don't search around for just the right red or green or blue, etc. Instead, you create the "impression" of those colors.
Instead of painting 'gold', you paint all the reflections of the surrounding areas, with a suggestion of a bright yellow here and there. This figure has lots of greens, blues, purples and reds as opposed to a bunch of different yellow tones.
I realize that this sounds very complicated and somewhat crazy, but it is actually a far easier way to achieve an effect, and you end up using a very small set of colors. As I have mentioned before, I seldom use more than 6-7 colors on an army, much less an individual figure.
This is also how I can work on several different genres at the same time. I don't need a 'clean' set of new colors for each figure... instead I utilize that one set of colors for everything, mixing where I need to.
Of course, beginning with the shaded basecoat technique helps a lot. This provides that basic framework which my first layers of paint used to on my 2D art. The idea was always to map out where the lights and darks should be as soon as possible, and then build around that.
These "golds" are made of oranges, greens mixed with tan, muted purples, dark blues, you name it. This variety in tones also makes it far more interesting to look at, just as looking closely at a 2D painting reveals all the interesting brush strokes of colors that were used to make you believe you are looking at something which is three dimensional.