I'd like to know how to achieve this painterly effect

[Damien Symonds]

You've got two layers named "BURN"   One of those should be "DODGE".

But as long as the blend modes are correct, that's cool.  Just change the name and you're ready to begin painting.

[Candi McGrail]

Oops, they are!  Great, anything specific or just paint?

[Damien Symonds]

Oh crap, sorry!  One more thing I did, I remember now.  I clipped a Hue/Saturation layer to each of the "DODGE" and "BURN" layers, with the Saturation slider at +30 on the Master channel on each of those layers.

Then yeah, just paint as you see fit.  Of course paint on the "Burn" layer where you want to darken, and the "Dodge" layer where you want to lighten.

This is what mine looked like:

[Candi McGrail]

Here is what I came up with...

[Damien Symonds]

I think it's nice!