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Linda,
The Munsell system is not necessarily just about neutralizing a color. That is merely one option. A color on your palette isn't the same as it appears when placed on your painting because the context changes.
The Munsell system, at least the way I use it, acts as a compass. If I place a color down and it doesn't look right, either the hue, value or chroma (or, in a worse case scenario, a combination of the three) will pop out to me. If the value looks too light, I'll darken it, or too dark and I'll lighten it. If it looks too gray, I'll increase the chroma, or if it's too intense I'll neutralize it. If the hue looks off, I'll go opposite direction. In other words, if a blue looks too blue-green I'll shift it towards a blue-purple.
I'm always thinking in terms of three dimensional color space, HVC.
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