SMP => Symmetric MultiProcessing. It's one technology for using multiple CPUs in parallel. In the x86 world, it's typically using two processors. With the right OS and right apps, you can dramatically increase performance by adding an additional CPU to the existing one in a system. Two 500MHz CPUs in parallel won't be as fast as one 1GHz CPU, but they may come close.
To take advantage of this, your CPU needs to be SMP-capable and you need the right motherboard. Windows 2000/NT and Linux are the two main x86 OS's that support multiprocessing.