Congrats on the new Mac
I've found quite a few apps that I really like since I switched just over a year ago, but on the Mac you'll find that most apps are paid-for. Usually they're quite cheap and come with free trial versions.
My personal favourites that I use most are:
Scrivener - very well thought out writing application, for serious writing
iWork - quite cheap (though not as cheap as NeoOffice) but very well polished. I love Keynote and Numbers, and Pages is quite good too.
TextMate - for HTML and Ruby coding
Aperture - because I've got a digital SLR. I shoot in Raw and this rescues lots of photos that aren't quite right. It's a pretty fantastic programme.
VMWare Fusion - I work on Windows, and I use Fusion a lot
Task Paper - Very simple but I use it quite a bit
Superduper - You can use Superduper to create a bootable backup of your Mac on an external disk. If your Mac drive dies, just plug the disk back in and it boots up exactly as it was! You simply can't do this on Windows.
There are others too, but I use them less - Microsoft Office Home is good but I like iWork, Omni-Graffle is nice but I hardly seem to use it, Adobe Creative Suite is of course the flag-ship of Mac software (and is much cheaper if you're a student) but I'm not a designer so it's not something I use miuch.
I doubt that list was what you were after, but you don't say what you want to do with your Mac. Firefox and VLC are excellent choices, by the way. Also, Mac The Ripper and Handbrake are good for extracting DVDs and converting them to iTunes format.
I didn't like NeoOffice at all. Maybe the new O

rg with it's native OS X version is better, but I've already got an Office suite.