It looks like a color correction effect. If you look at the whites, they have a lot of cyan in them, leading me to believe the color was shifted. To be sure, we would probably need to know more about the lighting used, such as the color temperature of the bulbs.
In photoshop, chances are, the sky was "corrected" separately from the player, giving the image that artificial look. I would love to hear from someone who knows for sure how this is done.
Shot with multiple flash units at various angles. This particular example is not that extreme. For a more "painterly" look, take a look at the work of Joey Lawrence for extreme post production or Dave Hill who does a lot of his work with strobes and compositing.
Aside from the compositing the people/QB/sky, I think the look is pretty much down to lighting and RAW development.
Assuming you get the lighting right, in Lightroom (I'm sure PS has the same controls, it's just not in my workflow), jack up the contrast and clarity, then use the fill light and blacks controls to clip/compress the image a bit. You can use exposure to adjust a bit if pushing up the blacks clips too much of the image. Drop the saturation relative to how much more contrast you add.
Then use HSL to fine tune - bumping blue/aqua saturation can look great if the clothes are those colors (while dropping the rest), and you can fine tune the tonal range of the skin by playing with red/orange/yellow luminance.
I'm not saying that's how that one was done, but it might get you in the ball park for the painted shiny look. Oh, and when you're done in PS, duplicate the layer (or stamp), and set this new layer to Filter->other->high pass with a value between 3 and 8, and change the blending mode to soft light (or hard light if you want to mask it back).