I just got a new computer today, I decided to get XP, but was sick of looking at the standard XP "Luna" theme. So I look into customizing xp for the first time. I didn't want to change XP dramatically or make it look like Vista. So I went for the "royale noir" theme. I added the Stardock, some yahoo widgets and a nice wallpaper of my favorite musician. I think got a nice fresh look and some cool new features. I realize for you guys this is pretty standard but I quite like it
Looks good for someone who just started customizing.

(I'll know people will yell at me for saying this, but...) Even I like basic Luna (and I miss it on Vista... :< ) But we all have to move on from the green & blue.
A good place to start your customization adventure is to check out some of the many ways to customize your PC all around the internet. And I mean other ways to skin besides WindowBlinds too. I started out customizing via regular .msstyles files and hacked theme service files. (Back then I wanted a Vista-ish look, so I used VTP as a base.)
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But anyways, here's my desk:

It's a combination of the Diamond & Think Green mycolors themes. My wall is
gaiety by mkorashy. I also have the
Vienna Rapture OD background, the
Harmony curosr fx theme, the Think Green weather widget, and
Libardo's AWESOME Dracon Rainlender skin.