Answer: There is a certain way he sets up his lead guitar and rhythm guitar tone on the tone switch.
Explanation: You can mess with the tone switches/volume of one of the options (it varies from model to model, I forget for the les paul), of either lead or rhythm, and switch between them for two different sounds. Try messing around with the tone switches and knobs in each setting and see if you can get a similar sound. Sorry if this answer isn't what you were looking for.
Visual learners might enjoy working through a process as they see a big amount of material presented before them that they need to take in with their eyes;)
