I just started to work with painter, so I cant really offer alot of tips, but the facial proportions are off a little bit.. maybe try sketching it out with a pencil using the facial propotion methods and then paint over it..
Looks like youre doing better than I am in painter with laying down the base colors, so if you work on proportioning things right, yuoull be in good shape..
try looking in the mirror while you do this...MORE....what i mean is...look at the color you see in LIFE...look at ANGLES...look at how light or dark things are..COMPARE....you have enough down to really work with it and work it out.
when i start paintings the colors are not accurate..nor are the drawing proportions...i correct as I go along...flip it horizontally...see it from a different viewpoint...make more adjustments.
pay closer attention to the mirror ok? ....really look..OBSERVE...relax...observe..make a few marks..observe again...
you should be looking in the mirrir more than you look at your drawing/painting...if not equally...ok?
ps...do a master copy...that will help...at least try one.
go to www.artrenewal.org and find a nice head to copy...dont sample the colors...judge them...paint...you will improve proportions and colors if you do this.
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work larger and try to look for "odd" colors in the skin. greens and blues show up and you don't even notice until you really really really look. And remember pieces don't have to be smoothed over to be finished, try doing a portrait with chunks of colors all over the place. Break out of the "smoothness = finished" mode and experiment.
One thing that helps me in painter and in photoshop is to reduce my portraits down to a thumbnail...a lot of times you can see the problem areas when you can take the whole thing in at once. This is along the same lines as Jason is saying but just something a little extra I have found.