I have been using XP64 for quite some time now, and for me, I have found it to be so perfect in almost everythign that I have no intention of ever going back to stock XP.
Its smoother, sleeker and as for HL2 having a lower FPS, I myself found this to be the opposite, and HL2 for me runs much much better in 64Bit.
For what its worth, I currently do not have the Catalysts installed, instead Im using the standard XP64 Drivers, and my gaming is great. I also know that one game I have asks for OpenGL, but Im unsure what that is, but BF2, Company Of Heroes, Need For Speed etc are all running better than they do with the catalysts, and this has allowed me to avoid the DOTNET garbage that I dont want either.
In terms of reliability, I feel that XP64 has not only caught up with XP but it has surpassed it... 10-fold.
Now, I feel that XP is too old and useless to be worth bothering with.... Vista on the other hand is a similar thign to XP... We have the 32 and the 64 bit versions, but considering that every single chip that is coming out these days is 64bit, even considering a 32 bit OS, is just ludicrous. Vista 64 will soon dominate the market, and it is *** way the market will be going... Vista32 is only out there just to get the cheap people who have not been bothered to upgrade recently or have cut serious corners by buying a cheap PC ( That probably wont be fast enough to run Vista properly anyway ) into the playing field.
No, 64Bit is the way to go... XP or Vista, it makes no difference really as long as its 64.
The question abotu what apps should you be using has already been answered.
I will add a couple of things though, that moving on up has forced me to abandon.
1 - MidiFile ( Specifically XG ) playback.
I cannot play XG Midifiles anymore. I have a few options... DB50XG on my TBSC. An MU10, or SYXG50, but XP64 an indeed Vista have stopped those.
2 - PageDefrag.
Loved this prog. XP64 and Vista once again wont play ball.
3 - Partition Magic
XP64 will run it, but not if it needs to shutdown and restart to do its jobs, but Vista hates it... Even after you get rid of Vista, any partitions that vista has touched, cannot work properly. I have lost data because of the way Vista can access its Partitions, and in fact, a short while ago, I sent off my Raptor to WD because of what Vista did to it, and even WD said that Vista had messed it up and they sent me a new drive!!! - WooHoo!