There all pretty decent....I prefer the 1st 5 albums w/David Lee Roth, but musically you can still find lots of great guitar riffs on the later stuff also. I think the best guitar stuff is found on their least successful/commercial release Fair Warning...that album really rocks hard, I would follow that w/VH2, Woman & Children 1st, VH1, and 1984. Here's just a few suggestions;
Ain't Talking bout Love
Hot For Teacher
Mean Streets
Dance the Night Away
Panama
*For a great instructional video that clearly explains Eddies technique and showcases a lot of his signature licks check out Kurt Mitchells In The Style Of V.H., It's well worth the money.