I have to warn you that there are only about a dozen episodes ever produced and it was intended to run much longer than that. Many of the characters have mysteries associated with them and they are never resolved. It 's possible that they might be in some upcoming presentation, but there are no guarantees that any such presentation will ever happen, even if it looks promising right now.

However, since you've never seen it before, I envy you, as you'll get to watch the episodes in the correct order instead of the order in which FOX decided to air them. Specifically, you'll get the pilot first, which many people I know consider to be one of the best things to have been presented on TV that year, despite that FOX decided to broadcast it last, after they'd cancelled the show.

And it should go without saying, but I'll do it to make sure: don't listen to the commentary until after you've watched all the episodes. They give stuff away. I think one of my friends got burned by that watching the Buffy DVDs when they referenced something important that happened two years later in a season not even released on DVD at that point.

Oh, and if you've never watched Buffy, you should definitely check that out, as well. More horror-fantasy, not sci-fi, but similar respect for characterization. (Were you pissed off at what they did to Lennier in the last season of B5, too?)