The three-way ladder match at Threemendous was unreal if you miss the old Hardys/E&C stuff.
Steen Wolf is the PWG Generico/Steen ladder match with a surprise at the end, also has the Young Bucks and Future Shock in a pretty solid stiff war.
The DDT tag tournament set is FANTASTIC. If there's one thing PWG does really well, it's tag team wrestling.
For a good intro to the company, go with anything BOLA, DDT, or the anthology (Sells Out) sets. I think the first may be out of print, but you might get lucky on Amazon.