It was in large part a social factor. Most of my first line leaders smoked in the Army. Most of my co-workers smoked getting out.
I had tried a few times without ever getting "hooked," until one random day it was about to rain. I was inhaling deeply (desert rain has a great smell), and took my deepest drag yet.
I finally realized I had been smoking in my "mouth" it, so to speak. From there the head-clearing buzz was present, and it truly felt amazing.
Then it started to go away. Take another drag, and never quite reach that again.
Years pass and you start to wonder why you still do this stupid, nasty habit. At this point, you're already addicted and like the beautiful light switch analogy another user gave, it is a conscious effort to always quit, not to pick it up again.
I somehow only picked up smoking a year after separating, not trying to insinuate a 1:1 relationship there. Now drinking... ;)