The 80's DVDVR Lucha set is great but I wouldn't recommend it as a starting point. I think the matches that are the easiest to appreciate from a higher worldview are the 8/31/86 Santo/Espanto Mask vs Mask match, 7/18/87 Santo/Casas Mask vs Hair match, 4/10/88 Santo/Espanto title match, and MS1 vs Chicana 9/23/83 (which you need to almost view through a lens of 1970's US in terms of using fewer moves but getting everything out of them.
For the 90's, the easiest entry is 1990 CMLL trios matches. The best 1990 trios matches are better than almost all of the trios matches on the 80's set. Then you get to Dandy/Casas from 7/5/92, Panther/Atlantis 8/11/91.
AAA is all over the place in the 90's (and really throughout it's entire history) but there are some excellent trios and atomicos matches from 1993-1995. Rey vs. Psicosis from 9/22/95 is also a good gateway into a lucha title match but with elements of Japan thrown in.