I only got into Neil Young last year, at the age of 35, and I have to agree that “Decade” is a great place to start.
The trouble though, is that he is not as good a guitar player as he thinks he is, so some of his stuff can be pretty hard work.
I tend to prefer the stuff where he concentrates on song-writing, such as After the Goldrush, the campaigner, a man needs a maid, cortez the killer, ohio etc the list goes on.