Given that a) most human rated rockets have had 0 flights before use, and b) I'd expect each starship to have at least 10 flights, and at least 100 in total without mishap before launching, the statistics should be good
(b) is true and should make it substantially safer than other launch systems. But given how narrow the margins are for something going wrong (zero ability to land safely with all engines dead, for example) it’s still going to be pretty dangerous compared to more mundane forms of travel.
A future starship could plausibly be the first rocket to fly to space unmanned, return, and then fly humans to space!