Slight correction - the PSU supplies both volts
and amps ...... but the voltage is the ''pressure'' to deliver the amps the unit is capable of producing (its total power rating in watts - amps x volts.)
Yes check current requirement for each item but - times that by the voltage of the device.
A ''Rail" is a term used to desribe a voltage supply line .. so a 12v 'rail' is a section of wiring or circuitry concerned with that specific voltage - likewise a 5v 'rail' is concerned with supplying that voltage to relevant devices.
Example - taking a set of figures from a hard drive I have to hand - it is rated 5v at 0.65A and 12v at 0.9A. So - this represents in power terms ...... 5 x 0.65 = 3.25W and 12 x 0.9 = 10.8W. Add these and we have total 14.5W. One of the more modest power requirements within a system.
In contrast however, things like graphics cards in particular can require much more power. Single cards might be around 25W to 50W but some higher end cards can go up to over 200W. You may have to do some search on your graphics card to find out its power needs. There is some useful info - here ....
http://www.atomicmpc.com.au/forums.asp?s=2&c=7&t=9354