People always talk about Barney being a crap singer and that he shouldn't sing JD tracks, but I can't think of too many NO songs that would haved suited Ian's voice, especially after Movement. I heard 'Ceremony' on Still first, but it was the NO version that really got me. Bernard's detached style was new to my ears.
Anyway, I had a haphazard way of getting into the albums. PCL was the fave for a long time. I bought Substance early on, but unfortunately subculture, state of the nation, and shellshock gave me the impression that Technique would follow in that vein. How I was so wrong! Technique is now the fave, but I'll still throw on Movement pretty frequently.
John Peel Sessions 81-82 and PCL are a fine place to start. The former has better versions of songs that appear on Movement, and that stage of the band is as important as the more synth-dominated work, despite what some may say.