there are only so many effects you can generate with styles alone,
  and even then the results of fine-tuned visual effects
  generated by Photoshop are often visibly superior to a
  limited version of the same effects applied using CSS.

I can relate there, but for me, on the whole, it seems easier to declare and manage the rules for style, size, etc. in CSS rather than in Photoshop, where the analogue feels baroque (aligning elements proportionally without numerous guides? clicking through layer styles...).

I hope there's a more programmatic interface/extension to Photoshop that I've been missing.