The thing is, you can be very good at something without understanding it.
Just ask them why they pick that certain color and you won't find rational behind it. They just...did, their hand just move to that color, paint it, and it looks good—the results of tons of practices over the years. Not to mention some artist didn't even have proper art education, not to mention art theory. Why and how it happened to be the same combination as in the color harmony theory is surely hard to explain.
The trouble is you can't teach the intuition.