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If you place a character bearing the third eye in the start up (placement) segment on the table,

do all subsequent strategems played by your opponent can they be rolled for to take an extra command point on a 5 or 6?

Also, is there a limit of cmd pts you can accumulate?

I believe - based on the most recent Custodes FAQ - that one he is deployed you may then roll for command points spent by your opponent. There is no limit to the CP you accrue.

Ok so if I'm understanding this correctly you can deploy your character with the Helm onto the battlefield as your first drop and then if your opponent uses any deployment stratagems to deepstrike etc you can then roll to get additional CP.

That is correct - again I'm basing this off the most recent Custodes FAQ.