The product spec says "This event will also be generated if the supply voltage is already below VPOF at the time the POF is enabled" but it seems like the event is not generated until after a delay, which the product spec does not seem to specify.
Attached is code I used to test, where I enable the POFCON and immediately check for the event, with or without an intervening delay.
There also might be a difference between the nrf51 and nrf52, since my code to check battery level using the POFCON (not the code attached) seemed to work on the nrf51.
Also, in nrf_drivers/hal/power.h, the function nrf_power_pofcon_set() does not flush the ARM write cache. So its effect would not be ensured until some time later, when the next RAM read occurred and flushes the write cache.
Environment: SDK12.2 and not using BT or softdevice, tested on uBlox NINA via NRF52DK.