I used to use Fireworks for nearly everything... I knew photoshop a bit, but it was always easier for web graphics to pull up fireworks.
Now, i'm going back to photoshop, just because of the superior filters. Fireworks used to be able to use photoshop filters, but no more. I guess adobe didn't like that.
Oh, and bryce and painter are good for backgrounds, and I especially like painter's clone tool, makes for some very interesting collages.