He was obviously looking for the right people for the right OS and programming languages at that time for highly scalable communication systems. Would be interesting to compare that with job offers of competitors of that time (who were those, btw?).
I think there were a few technical bookstores online, but he was one of the very earliest, and certainly the first to try to have a larger scope (e.g. before it was 'let's sell our inventories online', Amazon's idea was 'let's sell every possible book online').
Interestingly enough, Amazon was (if I recall correctly) started as a research project: David Shaw (of the hedge fund D. E. Shaw) asked Bezos (then a VP there) for a list of ways to make money online. At the top of Bezos' list was bookstores. Shaw decided it wasn't worth the risk, Bezos decided it was, so Bezos left the company to found Amazon. Shaw ended up starting Juno, though, so it's not a total loss.