My impression of the correlation between technical facility and scam resistance has been a little disappointing(it doesn’t seem to be completely absent; but it’s weaker than I would have expected); but it does seem unlikely that someone who does HR at a tech company is notably more technical than someone who does HR anywhere else.
Being the “Chief People Officer” might actually be unhelpful: people lower down the HR and payroll food chain get low-effort “plz reassign my direct deposit” scam attempts all the time, which likely hardens them to the realities of blindly transferring money; but a c-level is less likely to have gotten their hands dirty with that recently.