You won't like hearing it, but I think some work on the fundamentals is required before you'll be able to go much farther. How are your traditional skills? Sketching, painting and the like? I'd suggest doing some light study on topics like anatomy, colour theory, lighting etc.
Don't get the wrong impression: I don't want to implay that I'm a master of anything (god no, soo far from it), nor do I want to be discouraging, but even for stylized/cartoony stuff, a basic grip on anatomy is required and the anatomical flaws here are beyond minor...
Some tips on colouring/shading:
The main thing is to try to think about how the light would hit on these objects if they were 3d. In your original picture, the shading is basically a gradient thatflows from right to left (light on the right, gradually darkening toward left). There are thing to take into account along the way. Like, eyes are generally a bit sunken in the head (resting in the sockets), so shadows fall around/under the eyes. The nose sticks off the face, making the tip brighter (highlighted), while casting shadows across the rest of the face.. not the best explanation, but maybe someone else can clarify.
Contrast is your friend. In this pic, the contrast is a bit low, making it hard to distinguish between light and dark, and, in the end, making the image appear flat. Up the contrast (make your darks darker, your lights lighter), and the end result will be a much improved piece. Keep saturation in mind while doing this, too, ass really high saturation can make a picture hard on the eyes (you saturation levels are good here: not to low, or bland, but not too high and eye burning, either).
As for colours themselves, a technique that many people around here seem to use (myself included) is hue shifting. Hues shifting is, well.. shifting hues... as your colours lighten and darken. So for example, if your midtone was red, the shadows might be, say a darker purple while the highlight might be orange (in which case, your shadow's hue shifts toward blue, highlight's toward yellow).
Apologies here, 'casue a friend of mine walked in while I was typing and I lost my train of thought
I'll end it here... I did a quick and dirty edit, though, that covers Mich of what I mentioned (didn't touch the lineart).