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The key to color matching is the recreation of the relationships of a color to its surroundings. As Michele stated, perfectly mixed color will appear wrong if what surrounds it is off.
Bouguereau, who painted the most realistic and believable flesh tones ever, made no attempt to match "real skin color." It was his ability to recreate the correct relationships between the color changes within the painting that made his flesh so convincing. Anyone holding their hand up to one of his paintings would be suprised to see the great difference.
Copying a color exactly is a good exercise unto itself but it is far from the ultimate goal of color mixing.
To that end, I also teach my students to consider value first, then hue and lastly chroma. The palette arrangement I use makes this task a very logical one.
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