I use Skitch all the time. I use it mostly for quick screenshots (whole or part of the screen) and one-click sharing to a variety of services. But, you can do some simple image editing with it, too.
I never used Quicksilver, nor did I ever much use Spotlight, so I can't compare, but Alfred is really, really good and I believe does much more.
I hesitate to get into the whole "iPhoto vs. Picasa" issue, but depending on how you want to use/organize/share your photos, you can find tons of discussions just by Googling. iPhoto has a lot to offer, and if you're only going to use other Apple devices, you probably just want to stick with it. But I happen to be a Picasa fan, especially since my phone is Android and I don't have an iPad/iPod to coordinate with. So I'll throw that out there for new Mac owners, since many of them might have come from Picasa on Windows anyway. You can still use it on Mac OS, if that's what you're used to and you want to keep using it. Both programs are very good, but different. It just depends on what suits you better.