Newbie here, sorry for popping in. I own several MTV unplugged CDs, and most of them are extremely well recorded (IMO)....here are some recommendations
MTV Unplugged - 10,000 maniacs (With David Byrne on a 3 tracks)
MTV Unplugged - Alice in Chains
Unplugged - Neil Young
MTV Unplugged - Florence & The Machine
MTV Unplugged - Pearl Jam
MTV Unplugged (UK) - Stone Temple Pilots (with Scott Weiland, very hard to find)
MTV Unplugged - Alanis Morissette
Unplugged and Seated (Having a Party) - Rod Stewart with Ronnie Wood
In Concert/MTV Plugged - Bruce Springsteen
No Quarter (MTV Unleaded) - Page and Plant
Unplugged (Live at Hull City Hall) - Liam Gallagher
Not MTV unplugged, but a favorite live recording Little Feat - Waiting for Columbus