Yes, Access can be used quite nicely for an HR database. I did a google
search, and found there are many companies that are willing to sell you the
rights to use their HR database software. I did not see anything resembling
a sample program. This is probably because HR is a complicated field, and it
takes a lot of effort to put together a decent database for a specialized
application like that.
No matter what you use for an HR database, you should put the computer(s)
that run the database behind a hefty firewall, or better yet, not have them
connected to the outside world at all. HR information is very sensitive, and
should be protected. Just putting passwords on a server share, or on the
database, is not enough.