Firefly order
^ That might be something to do after you've seen it all the way through once, but I think watching it that way to begin with would confuse a new Firefly viewer.
I stated that "obviously" was perhaps too strong of a word.
As some have pointed out that they didn't start getting into it until disc 2.
By this, what they mean (I think) is that the 2 part pilot (Serenity), second pilot (Train Job) and Bushwacked which comprise the 1st disc are a bit slow as there is a lot of exposition to set-up.
The airdate order:
The Train Job - disc 1
Bushwacked - disc 1
Our Mrs. Reynolds - disc 2
Jaynestown - disc 2
Out of Gas - disc 3
Shindig - disc 2
Safe - disc 2
Ariel - disc 3
War Stories - disc 3
Objects in Space - disc 4
Serenity pilot - disc 1
Trash - disc 3
The Message - disc 4
Heart of Gold - disc 4
Serenity movie
Forgive me, but I'm actually going to defend the airdate order a bit.
Yes, I know - heathen.
Airdate order front-loads some of the better episodes and why they were shown out of order this way.
Train Job services to give enough exposition for the characters and explain that these aren't necessarily the bright and shiny good-guys you would normally expect.
Bushwacked I would personally put off till later (after Out of Gas maybe) since it is backstory on Reavers mainly.
Our Mrs Reynolds is a nice light-hearted romp and some excellent characterization.
Jaynestown at this point has enough on Jayne's background from the previous 2 episodes (or 3 if you did watch Bushwacked) to give the viewers a nice perspective on the machiavellian mercenary.
Out of Gas at this point tells a lot of backstory and shows the love Mal has for his ship along with the interactions of her crew toward each other.
In DVD order this does not come until much later.
From this point on you have enough information to understand the characters for the remaining episodes.
Yes, the order is screwed up. Yes, not all of the plotlines unfold in proper order. But, this is also the way the 1st generation of fans fell in love with this series as well.