When we did our extended 200+ hour test, we saw the percentage decreased slightly each day. I think the first day off-grid, the Powerwalls were charged up to 96% but then on subsequent days they only charged up to 95%, 94%, etc. When we ended the test, I think they were only charging to 88% or so before they would raise the frequency to shut down the solar system.I dont think thats what happens, based on what I have read here. Havent experienced it myself yet, but from the reading I have done here, with grid power OFF, if the powerwalls hit somewhere around 94-96%, they trigger the frequency to shut the PV system down. Some inverters have the ability to "ramp" down (see post from @GenSao on subject). Otherwise, the powerwall just tries to shut the PV system down.
As you mentioned, I did charge one or two cars during the day when solar was at its peak. I sometimes do that even when the grid is up. It's just nice to be able to charge directly from solar, even if I miss out on a few Netmetering credits.