How exactly does Elemental Overload work where it usually does more damage than chain lightning? Does each proc make another chain lightning? I’ve noticed lightning sometimes does too, so can it proc off of itself? If so for how much?
When overload procs it does 85% of the damage of the spell that overloads. In your case chain lightning. You are seeing crits on them that makes them higher damage. And yes it copies the spell used. In this case you get to be a Sith Lord with the chain lightning
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Also, with Stormkeeper/Surge of Power talented, Lightning spells can have more than one overload, so the overall damage of overloads gets higher than the base spell cast.
To add to this - if you somehow manage to get your mastery above 100% every point over 100 is a chance at a 2nd overload from a normal cast.
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So reading the other comments idk if everyone knows this, chain lightning works with elemental overload differently. Instead of being % per cast the % is split per target. If you have 100% overload chance and 5 targets it will be a 20% chance on each target. So it is likely you are getting more than 1 overload per chain lightning. This does not mean you have a 100% chance per cast at 100% overload chance but in 100 casts its more than likely you get 100 overloads off. This also leaves room to get up to 5 overloads off a single cast.
I am using information from old versions of how mastery worked while also checking for updates and have not seen any. This means having over 100% master either off proc or trinket is not a waste. Single target, another shaman listed correctly, overage has a chance to have an extra overload, but this also increases the chance of the multiple chain lightnings.
I personally have a theory that the totem mastery buff applies to each jump separately making 100% mastery grant 25% overload per jump.
Please correct me if you find my information incorrect. I believe my information is supported as the overload for chain lightning isnt always the first target, it may scale different than the 20% on each target but i beliefe each jump has a separate chance that is not equal to the mastery %
Torchwick-Darkspear if you have any questions
Thank you for posting this. I was going to post something similar, however all the information was older info without any new updates as you said.
To update, single target Spells cannot overload twice, i got my mastery close to 160% and not a single double overload
Awwww. That disappoints me so much. 
I know!!! It kills the class fantasy just a little! Id love for mastery to have no cap and see if i can do an overload build! It would be so easy to do too! Its hard to break 100% on mastery but if someone wanted to why not let them, it’s literally the worst stat in meta right now (i still stack cause pretty)