Sure!
1. Well, first I made a copy of the background, and applied a 'Surface Blur', with a radius of 8 pixels and a threshold of 22. I thought this made the effect a little too strong, so I faded it down to about 40%. I also erased most of the layer, around the hat and hair, so that the blur was only present on the background (which was a bit noisy), and the face. I love the surface blur for making skin appear smoother, moreso than any of the other blurring filters.
2. I made another copy of the background, and used the patch tool to clean up the face a bit more, toning down the bag under her eye and a few other areas. I also dodged and burned around her face some, to help even out the skin tones. This part took awhile, as the longer I stared at it, the more I kept going back and forth between convincing myself I was going too far (at which point I'd pull the effect back by lowering the opacity of the layer), and not going far enough (making me bring the opacity back up). I was especially careful around the eyes, which I felt needed some brightening, but I was trying really hard not to make it seem unnatural (not entirely sure if I succeeded, there).
3. Made another new layer, this time only containing the hair, neck, and hat. Did lots of selective burning/dodging here, too.
4. Made a new layer and basically repainted the background. I really liked that red color in the background, dangerdoormouse, but just wanted to see more of it.
I put all of the different elements I was editing into seperate layers over the top of the untouched original, so that I could play with the opacity of each until I got just the right balance of all of it. Then I finally flattened the image.
5. I made a copy of the background again, and set the blending mode to "Soft Light", and played with the opacity until it was where I wanted it. As I said earlier, this really helps boost the color and contrast. However, it also made her skin tones kind of yellowish, so I played with the 'Hue/Saturation' on the background to compensate for this. Then I flattened the image again.
5. Finally, I added a vignette. I made a really rough, circular selection around the edges of the image using the lasso, selected the inverse, feathered it by 40 pixels, and used the 'lightness' slider in the 'Hue/Saturation' box to darken the edges. Then I deselected the selection and burnt the edges a bit more. I pretty much put a vignette on everything portrait I make, now - A tip I got from 'Christie Photo'.
6. And last, I applied the 'Unsharp Mask':
Amount: 99%
Radius .7 pixels (but on a full-sized image, I'd have this closer to 2-2.5 pixels)
Threshold: 3 pixels
This is pretty much my whole shtick, that I run through with most of my own portraits as well. I'm not even so sure I like everything I did with dangerdoormouse picture though the most I look at it. I dunno what I'm doing half the time, but I was just in the mood to play around in PS this morning, and trying to help.
Nice pic to start out with, dangerdoormouse!