CSS3 or webkit extensions or mozilla extensions != CSS. I would never use any of those methods (for say, the next 2 years or if it was only a personal site I didn't care about and not a customer site).
Also the learning curve to do stuff faster with Fireworks than Photoshop is maybe 30 minutes, it's that simple.
I'll disagree and say that Photoshop is faster and simpler, why? Because I'm better with it.
Use whatever graphics program you're best with.
First of all if you're only using gradients and layer effects like multiple borders most of that stuff can be done with CSS now.
The links below are for buttons and shapes but you can apply those effects to anything:
http://blog.anomalyinnovations.com/2010/03/creating-a-realis...
http://net.tutsplus.com/tutorials/html-css-techniques/build-...
http://net.tutsplus.com/tutorials/html-css-techniques/quick-...
Also photoshop is just as competent at saving images with those effects if you convert it to a smart object and rasterize it first.