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2021 Rav4 Prime max trim
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Why and when a R4Prime turns ICE-on can be a great mystery. Check out the long list of know/unknown conditions that can cause unexpected ICE-on events in the Owner’s manual. You found the front defroster ICE-on trigger. You can also experiment with adaptive cruise control, and paddle shifters that when regen-ing (too much) can trigger ICE-on also.

That sounds like some confusing Overhead backlit button functionality, unless you are just saying that when the R4P is not in READY or IGNITION ON all backlight buttons are lit, and when you turn R4P off they turn off too.

Carista beta app has some interesting settings that will allow special window/moonroof opening/closing operations after you turn R4Prime off. You can open all the windows and moonroof via key FOB, and close all windows/moonroof with physical key lock-turn. If you turn on these functions, you must accept the risk of unintentially press and hold FOB Unlock to open all windows and moonroof and let Mother Nature in (Murphy’s law indicates it will be during a rain storm).

Battery mystery needs more details. How did you see that it had full traction battery after charging SAT? How did you verify that the big traction battery (not 12v) was too low for EV mode? It will start the ICE for a ton of reasons besides low traction battery. There have been posts about (near) first charging sessions taking longer than normal, maybe because it is conditioning the new traction battery.
 
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