Sounds like you'd want the following for each pool?
Balancing -> Balancers -> only SSD Optimizer ticked
under Drives, tick the SSD / Archive drives as appropriate to set your cache drive
under Options, set sliders as desired (these only concern filling, they don't empty)
under Ordered placement, leave both Unduplicated and Duplicated unticked (or, if you want to use it, make sure "Leave the files as they are" is selected).
Balancing -> Settings
under Automatic balancing, select Balance immediately, with the "Not more often than..." unticked
under Automatic balancing - Triggers, select 100% / unticked (as you want it always moved straight away)
under Plug-in settings, "Allow balancing plug-ins to force immediate balancing..." ticked (so it should move straight away anyway)
under File placement settings, should be irrelevant since you're not using the File Placement section.
This should result in any files copied to the pool going via your SSD cache drive first then being immediately moved to the others. As always with "production" data, I recommend confirming the behaviour is as expected with a test pool.
