I think one of my favorite GBV albums is not really a GBV album. "Speak Kindly of Your Volunteer Fire Department", which is Pollard and Doug Gillard is absolutely amazing. It's so good you'll be angry and sad that there are not more Pollard/Gillard albums (well, hell maybe there are, the discography is just too damn huge).
Robert Pollard With Doug Gillard - Larger MassachusettsNow I will be listening to this album for the next two weeks.
As for live shows, I saw them at the Stone Pony for Universal Truths and Cycles. It was truly amazing. As for those that might complain about the "quality" of the live shows, I'm sure it varies due to the tremendous amount of alcohol ingested during most shows. So it's probably a bit of a luck of the draw thing. The one guitarist that I just call "Drunky" (Nate) was plastered, but the rest of the band was damn solid. If I'd have missed that show I'd be a real chump.
Also for an alternate sort of "Greatest Hits" take, grab their appearance on Austin City Limits. It's bizarre.