A simple thing that I have used to help me out (in my work with cinema
projection and video editing) is:
RGB is a *transmissive* specification. It is used a lot where the light
from the image is being *generated* by that image...
like a CRT. It
*makes* the light.
CMYK is a *reflective* specification. It is used where light is bounced
off a colored surface, like a magazine page. As was pointed out, mostly
used in the printing and graphics arts.
And there are of course many other flavors and types of specs - and we
won't get into 'brightness' and all that entails...
So if you're trying to match paint - a 'reflective' specification would
be the most accurate, I would think.
Cheers
John