If you connect the two DT25s with L6 Link:
When you change from channel A on either amp, the other amp will change to the same channel, i.e., both amp will always be on the same channel. So if you attach a foot switch to one of the amps, both amp will change channels. You can use MIDI to program each topology of each amp individually to be whichever amp you want if you have updated them to Version 2.0 firmware. You will be limited to eight amp types on each amp. The DT Version 2.0 firmware does not include the Model Packs available for the POD.
So if you know what combinations you want, you can pair them up. Additionally, if you change the Topology I-IV, Class A / AB or pentode / triode setting on one amp, it does not effect the other amp.
As a side note: The beauty of the POD HD500(X) if that you can set up each DT (up to 4) to be whatever you want, including the Model Packs if you buy them, at the press of a foot switch, in addition to many other other effects and connections.