Devices powered from the 2nd LDO power down when the ESP32 goes into deep sleep

That’s correct! LDO 2 is tied to both a user controllable IO and VDD for the Flash/PSRAM, so when the ESP32-S2 & ESP32-S3 goes into deep sleep, it automatically shuts down LDO 2 for you, so you don’t have to remember to do it yourself.