First steps at "real" web bling

You'd not know it from the looks of this blog, but I'm starting to play with "real" web design stuff. You know, fonts that aren't available on the web for title bars, buttons, etc. Yea, image replacement. Ahh well, I guess it's time to stop thinking that purist views can be pretty too. Along these lines, I've cracked out Illustrator. It pains me to do stuff in Photoshop for some reason -- too limited, things don't scale properly, etc. I'd love to hear about any open source tools that can do the steps of "make it pretty", "edit it easily", and end with "save slices out to individual files." Ideally with "write all the XHTML and css files for you in a sane and reliable way."