This photo has more processing on it than any I have ever done before. I saw a similar photo in a photography magazine and set out to recreate it.
This is my wife. I promised her flawless skin so she agreed to sit for me :)
To start I had to get her to put on make up in a different manner. She went heavier on the mascara, more eyeliner, she drew some in her eyebrows as well. The last thing was some bright lipstick. Later I found a glossless lipstick would be better. I needed the make up to make sure her features stood out.
I lit her with two softboxes on studio strobes in a fairly standard manner (45 degrees from front and above her). You can see them reflected in her eyes.
Once I picked a photo from the many dozens I took ("I thought this would only be 5 minutes?") I did a few things to it.
Working at first in Lightroom I checked the white balance and adjusted a bit. I increased the contrast a lot and increased the clarity. I also clones out anything that may show up later (she had a small red spot under her eye), and I used the adjustment brush to soften her skin. I also used this to enhance her irises a bit to make the colour stand out more.
From here I left Lightroom. For those that do not know, this is rare. Since I do not do much outside Lightroom, I only have PhotoShop Elements, but this was enough.
I added an adjustment layer to increase the contrast again.
I added a B&W layer and set the light to hard.
I added another overlay layer and used the paint brush tool to paint out anything I did not want with white.