Subtractive color theory is useful, but it is not the end all story. In theory, subtractive colors can be used to describe a remarkably wide gamut of perceived colors. However, the actual color spectrum is continuous. Real lighting situations can lead to situations where two colors which matched under one lighting can be visibly different under others. This is one of the reasons why spot colors exist: they are a single understood pigment, rather than just a "color."
Indeed, if you look at modern printing technology, many printing methods offer more than 4 colors. 6 or 8 color processes are common, offering room for a larger gamut of colors.
The color we perceive is always a function of the color of the lighting and the absorbtion spectrum of the object. Makeup artists know this, and have figured out the correct pigments to use to accomplish various goals. This is also why it is advised that people picking out colors for their house view the colors at several times of day, as the color of light shifts during the day and that can affect the balance of colors in surprising ways.
If you really want to get into what we actually perceive, it's worth looking into the sensitivity of our eye to color. It is also worth looking at some of the neurological models of color which we have developed, such as opponent process theory.