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

I don’t think (a) is true. The Shuttle flew with people on its maiden voyage, but that’s the only one I can think of.

(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.