Different PC parts need different voltages. A wall socket only gives one specific voltage, depending on where you live 120v, 130v, 230v or 240v. All of those are way too high for PC component, so the PSU converts the power to lower voltage DC power. Some components need 5v, some need 12v, etc so a PSU has a 12v rail, a 5v rail, a 3.3v rail, etc to deliver the right voltage to the right cables.
The actual amount of power that the PSU can deliver is determined by the maximum amperage on each rail. High amps on the 12v rail is by far the most important, followed by the 5v and 3.3v rails.
Some PSUs have more than one 12v rail, because it can be easier/cheaper to implement multiple lower amp rails than one high amp rail. Single rail used to be better, but a quality PSU with multiple 12v rails will perform just as well as a single 12v rail unit these days. No need to worry about it.