The point of a Tank's "opener" is (i) to grab initial aggro as quickly as possible, then (ii) secure that aggro as quickly as possible and finally (iii) cycle through any abilities that will maintain aggro, enhance your survivability and reduce the fight time.
For a PLD, this nearly always involves opening via using Flash at least once on >1 mob, and then repeatedly using Flash (>3 mobs) or cycling the RoH combo (<=3 mobs); plus whatever useful off-GCD abilities are available. Shield Lob (or even Provoke due to its longer range) can be useful to grab initial aggro on ONE mob at a distance, but it's often better just to run in and Flash whenever there are multiple mobs to worry about and nobody else has yet pulled hate.
Once you have a decent lead in hate levels, you can start getting more fancy - spending a GCD to throw up Stoneskins and Shield Swipes/Bashes etc as long as aggro is maintained (RoH combos or Flash + Riot Blade, depending on how many mobs you're facing) ... but that initial pulling period is very important for locking down aggro ASAP.
Stoneskin applies a barrier equal to 10% of the targets MAXIMUM HP (18% in the case of the traited WHM version). Your current HP doesn't matter.
As a PLD, SS is fantastic to cast on yourself any time you could use an extra "buffer" of survivability... assuming that you are already well ahead in the hate tables.
The only downsides are that it uses quite a lot of MP (recoverable via Riot Blade) and it has a long and interruptable cast time (3 seconds).
The long cast time means that you often need to cast it proactively whenever you know a big hit is nearly about to occur, rather than waiting until you see the enemy start to charge a big attack.
It should be noted though that raising your Vitality and using Bulwark (Block rate increase) can reduce the chances of a Stoneskin cast being interrupted... this is because SS casting will not fail unless you take a certain % of damage during the cast time, and a blocked attack cannot interrupt you (unless you get hit by a status effect such as Silence or Stun).


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