Photoshop can do a fair job of removing the background but only fair. Using chroma key green or blue doesn't matter in PS, just helps a bit.
If you waant to get serious about it, download a trial version of Primatte. It's the best for background removal by far. Bit of a pain to use and not as fast as some competing software but it does the best job.
Primatte Chromakey 3.0 Software : Adobe Photoshop Plugin :: Digital Anarchy
Be sure to download and view all the tutorials. It is absolutely necessary.
Even lighting on the background and separation to background are very important.
There are lots of people shooting Green Screen. Good luck.