I'm surprised none of the other answers give this reason:
Do you need it to connect? (or, how badly do you need it to connect?)
Consider this situation in Gen 4 (DPP) Pokemon:
- You: a 100% health 252 SpA Modest Life Orb Moltres currently active.
- Opponent: a Steelix currently active, and a 69% health 248/0 Milotic in reserve.
Your Moltres knows Fire Blast/Flamethrower, Air Slash, Roost, and Hidden Power: Grass (basically the standard Moltres set). Obviously both Fire STAB moves knock Steelix out if it stays in, but of course opponent knows this. They could leave Steelix in to die and get a free switch in, or they can switch to Milotic. The latter move is the much riskier one for you, because it means the opponent gains the initiative if they succeed. Accordingly, you want to use something that is maximally effective against a Milotic switch while still being OK if Steelix stays in. Notably, if your opponent switches to Milotic, you get two attacks (since Moltres outspeeds Milotic), and opponent regains 6.25% health (because of Leftovers).
Here are the damage calcs:
- 252+ SpA Life Orb Moltres Fire Blast vs. 248 HP / 0 SpD Milotic: 111-132 (28.2 - 33.5%)
- 252+ SpA Life Orb Moltres Flamethrower vs. 248 HP / 0 SpD Milotic: 89-105 (22.6 - 26.7%)
- 252+ SpA Life Orb Moltres Hidden Power Grass vs. 248 HP / 0 SpD Milotic: 176-208 (44.7 - 52.9%)
Analyze these numbers carefully. If your Moltres has Flamethrower and your opponent switches to Milotic, you can fail to KO with the subsequent HP Grass. This means your opponent's Milotic gets to attack back or use Recover. On the other hand, if your Moltres has Fire Blast, and it connects, your Moltres will likely win.
Accuracy is not a factor here. If you use Fire Blast and it misses, then you are not KOing Milotic, but if you use Flamethrower, you are still not KOing Milotic, so it's moot.
Put another way, the average damage output matters less than whether the total damage output is sufficient. If Fire Blast has a 100% chance to KO the opposing Pokemon if it connects, while Flamethrower will only do 90% of the target's HP, would you prefer to have Fire Blast or Flamethrower? Sometimes it'll be the latter, but most of the time, it'll be the former. That is why people use Fire Blast.
Edit: as an addendum, it's worth pointing out that if you are running a Baton Pass team, then each move on your BP receiver needs to be 100% accurate, because you cannot afford a single miss (in general if the BP receiver dies, the rest of the team crumbles). See:
One Pokemon on your team should be your receiver, the Pokemon who is passed the boosts your Baton Pass chain has gathered. When this Pokemon gets +6 in the attack stat chosen to use (or some mixed sweeper equivalent), it should be able to OHKO every single Pokemon on the opponent's team with 100% accurate moves, since one miss can mean big trouble. Your receiver should also not be 4x weak to any priority move, and it might be helpful for your receiver to also have Baton Pass, but fitting it onto your receiver's moveset can be difficult while simultaneously trying to OHKO every single Pokemon on your opponent's team. Immunity to Toxic Spikes is a great thing to look into, and if your receiver needs to use a Life Orb to get certain KOs, it should be immune to sandstorm as well due to how common it is in OU, or else it can be stalled by good prediction on your opponent's side.