It's for an icon I made a while ago, so sorry if it's not exact.
We're going from This picture to this:

I use photoshop 7.0, but it's probably translatable.
Okay so we start with This picture of model Alex Bardenfleth.
1. Crop, Resize.
2. Sharpen once, and blur just the skin on a setting of 12%.
3. Take the burn tool and outline the eyes a few times, until it gets to a point you like.

4. Create a new layer, and pick a color for the eyes [I used 113D5C or something similar] color in the irises, and set this layer to multiply on 100%

5. Create a new layer and pick a hair color, [I used something like 27221B] set to hard light at 50%

6. Create another new layer, color the skin [I used DECAB3 I think.] and the lips [E4B7C0 or something close.] set to multiply at 70%

7. Create yet another new layer, and use the same color [E4B7C0] and go over the lips again, setting this layer to color burn at 60%

8. Flatten the Image.
9. Add a texture you like, set to color burn at 60%
10.Take the eraser tool and get rid of any part over your subject.

The End!
I'd love to see what you guys come up with!