For the Pokémon, I use the Dream World artwork but you can use whatever you want. When you think you have a nice layout, add a Gradient Overlay and a Drop Shadow. The latter should be subtle and not distracting, but still clearly visible.
Here's what I do for the gradient: Put on the default black/white gradient, set the scale as low as it can go and position it as close to the middle of the graphic as you can. Then set the scale of the gradient to a point where it is white at the top and black at the bottom. Lastly, set the blending mode to Color Dodge and lower the opacity to somewhere between 25% and 50% depending on the 'mon. You can use any value you want, but there shouldn't be any color distortion (i.e. sudden spikes in brightness between pixels); set it to the highest value you can think you can go without getting that distortion.
Keep doing what you're doing for those backgrounds, they're looking good.
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