Hi Sam!
Not to worry...I had the same questions when I started using PS and calibrating my monitor.
First, you should always calibrate your monitor, preferably with a hardware solution such as Pantone's Huey. It's cheap and does a great job if you only need to calibrate one monitor. Otherwise you can use the computer's manual calibration. (Are you on Mac or PC?) Pay particular attention to the gamma settings if you're on a Mac. (2.2 is usually the best one to choose.)
There are three RGB settings that you really need to be concerned with unless your printer has a specific profile:
- sRGB: The setting that incorporates the least amount (i.e. baseline, across-the-board compatibility) of color, but is usually the standard profile for lab submission
- Adobe RGB: A wider colorspace, much better to use while editing, and some labs even take this profile as well
- ProPhoto RGB: The widest colorspace, which would be ideal to use while editing, though you may see a de-saturation of some colors when you convert to an sRGB profile to send your proofs out.
Calibrating your monitor and setting the profile in PS are independent of each other. You should always have a calibrated monitor, which will render accurate colors while using any of the color profiles in PS.
I hope that helps with your question...let me know if you need clarification on anything I said.
There are also a lot of great resources online (well, you know, apart from OSP

), such as
photoshopguys.com, who also have a great video podcast. They also have many, many links to other online sites with informative articles about the mechanics of PS.