Earlier footage indicates the first man shot was attempting to start a fight with the militiamen, but there's a gap in the timeline where nobody was filming before the fight broke out.
The NYT has a very good article on the subject (and I'm a man who's very critical of the NYT)
OK I found a video showing the first fatal shooting [1]. It's not as clear as the video showing the mob chase (where it indeed looked like self defense) but from what I can tell the person who died got shot while running away from the shooter (it's hard to tell where the shooter is exactly during this time). Doesn't look like self defense to me. Hopefully there are better recordings of the whole incident.
Update: I take it back what I said. I found another video [2] that clears the picture. The guy wasn't running away from the shooter, he was chasing the shooter and throwing something at him. He then kept running after him and the shooter turns around and shoots him. The confusing part is that she shooter is shown coming from behind after the shooting happened. But it's because he goes around the car after the shooting and comes from the other side. I now believe all the shooting he did that night was self defense. He wasn't supposed to be there and play police but that's a different story.