No Western is complete without a healthy dose of cowboys facing off in the main street of some town, hands hovering over their pistols and squinting at each other intently. Usually, there's also tumbleweed involved.

Red Dead Redemption 2 has its fair share of duels, them being featured in both main missions and side missions prominently. An entire quest is aimed at tracking down and defeating famed gunslingers.
If you need to up your dueling game, here's a run-down.
Instead of simply being a one on one scenario using the standard game combat system, duels in Red Dead Redemption 2 are multi-phase mini-games of sorts. The first phase is drawing. Here, you need to gently press the pressure-sensitive R2/LT to fill the circular gauge. Press it too quickly and you ensure the opponent fires first. Press it too slowly, and you'll barely have any time to aim in phase two. This is a purely precision-based action so no written advice can help beyond 'don't immediately press the button completely'. With a bit of practice, it shouldn't cause any issue.
Phase 2 is aiming. As the first phase ends, the combatants draw their weapons. Dead Eye will automatically trigger at this point (regardless of the state of your core) allowing you to pick where to aim. Your performance in phase 1 determines how much time you have for aiming in phase 2. If you want to shoot to kill, aiming at the head or the center of the chest, however aiming at the opponent's drawn weapon may let you disarm them without killing them. This can be done to maintain your honor rating, or some missions may require the opponent to stay alive.
Once aiming is done, the last phase comes - firing. This is simple, you just shoot where you've aimed in the previous phase. The pressure with which you press the button here is irrelevant, you can just simply pull the trigger. If your aim was true, Arthur will fire before the opponent and strike them where you intended, winning the duel.
The only part you really need to pay attention to is the first phase. If you practice and get your timing right during the draw, you'll always have plenty of time during the aiming phase to target whatever area of your opponent you wish and some to spare.
A simplified version of the drawing mechanic is accessible during regular gameplay when not in the duel minigame. The same action - pressing R2/LT - will cause Arthur to quickly draw his sidearm and automatically trigger Dead Eye. This is a good opener to an encounter you've been expecting as it allows you to get the drop on your enemies, and pick off a few of them - or just disarm them - right off the bat.
Don't forget to squint dramatically. You're not a real duelist if you miss that part.