PCT = Single system (rarely do you get more than 2 CPUs in a system, so roughly 40-60 cores or workers max). Actually, I recall hearing something about a hard-limit to number of workers in PCT - forget what it is.
EDIT: According to this answer, after R2013b, there is no software limit for PCT, only your physical core count.
MDCS = Cluster. You pay for a certain number of workers, and you can then use that many on any number of systems. Theoretical max of infinite workers, but more like 1024-4096. MDCS requires PCT.
I believe MDCS uses all the same commands as PCT (MDCS does not come with its own), but certain commands are more PCT friendly and others are more MDCS friendly.