The most amazing console command, IMO, for taking great screenshots is:
This pauses the game, but allows you to move the camera around in real time, so that you can get amazing screenshots of stuff like combat, kills, etc from any angle you wish. Some of the coolest screenshots I've taken were done with this.
(Note that using TFC 1 during VATS combat can result in the screen being blurred out by in-game imagespace FX)
I also recommend lowering FOV for certain screenshots, like character close ups. Type in:
FOV 20 (any number between 20-45 will do, depending on how you like them).
To reset FOV to default after doing this, type in:
This is a screenshot done with FOV 20 and TFC 1: