According to [1], the S24 has gone all the way up to 4.45V.
[1]: https://old.reddit.com/r/techsupport/comments/1ayqveg/samsun...
I used to build quadcopters around 2015, and some of the battery mfgs released "LiHV" batteries, which were supposed to be safe up to 4.35v, however if you actually charged them that high, they would puff up like balloons after only a couple flights. Maybe with the cumulative advancements in the last 10 years, they've been able to push up the max voltage more safely.
The arbitrary value is what voltage you stop charging at. You set your maximum cell voltage and stop charging once you reach that voltage AND input current is below a threshold. Once charging is complete, you store the current energy value as the latest full capacity. That value then becomes the 100% mark.
Remember that batteries lose capacity over time. You must continually scale your state of charge percentage to the actual state of the battery.
The final charge voltage is a tradeoff between safety, longevity, and usable capacity. Higher voltages squeeze a few more joules into the cell at the cost of much faster degradation and increased risk of catastrophic failure.
A cycle count figure on lithium cells is pretty much worthless. It depends quite a lot on exactly how you cycle the battery. A 100 to 0% cycle is much, much more damaging that a 100-50% cycle. Higher currents and temperatures degrade the cell faster. Most cell manufacturers I've seen do give cycle counts under specific test conditions, but that's hardly applicable to real use cases.