Things I remember being blown away by..
Frontpage 2000. When I was a youngerster and playing with what I had on my computer, this program opened a lot to me. I loved being able to switch back and forth between the coded mode and the viewable mode. I did learn some bad practices at first... the <br> tag was new to me later as I'd copied FrontPage's insistence on <p>nbsp;</p> instead, for instance. But it was what set me off to look at anything relating to hacking.. ;)
Netscape 6. It sucks as we see it now, but the integrated suite was so much nicer than the older versions of Netscape and the AOL-based thing I'd used. The mail client was phenominal to me, having used Outlook before, the web browser feeled so much nicer and more modern, and so on.
SuSE Linux 9.3. The first Linux distro that became my main OS instead of just a plaything. It perfectly supported all of my desktop's hardware and made me fall in love with Linux and especially KDE 3.x.
Amarok. This was the first media player that I really loved. Unfortunately it's been messed up badly with the release of KDE 4 in my opinion.. I've yet to try the backports. But after playing with stuff like Musicmatch and Media Player on Windows and then JuK and the like on Linux, Amarok seemed just incredible.