PhotoShop7 Tutorial - Muted Colors

I've noticed a lot of black 'n white icons with one brightly colored accented focal point popping up. I really like them... but, I have a thing for the muted. The following will be showing how to make a muted color icon with a stand out, yet also muted, focal point. I'm also of fan of simple subtly. So, tonight we'll be going from
this: to this:

For PS7, not sure how translatable it is. Fake cut to my icon journal: adis_blends
Isn't TV's Randolph Harrison adorable when he's all pensive?