You want to use the pre-out jacks to conect an external amplifier.
'Pre-out' stands for pre-amplifier out. The pre-amp is the portion of the receiver does the switching between sources, amplifies the signal from the source a wee bit, controls the volume and tone controls, etc. It is *before* the amplifier hence its name pre-amp. So if your dvd player is connected to the receiver and your external amp is connected to the pre-out jacks, the signal from the receiver goes to the external amp first.
'Main-in' rarely exists anymore, but it is the opposite of pre-out. It is a way to bring the signal back into the receiver. If your receiver's pre-amp did not include a processor (like Dolby Digital, DTS, etc) you could use the pre-outs to send the signal to the external processor and then from the processor back into the receiver to be amplified by using the main-in.