Don't learn Photoshop."I want to be able to rely on myself for cranking out your standard web/app elements."
I had the same problem (learning Photoshop) with that exact reasoning a year ago. I learned Photoshop and got pretty decent with it in terms of what I could do, although I was far from able to design anything beautiful.
Then I learned there is a much better way for us developers: buying templates.
If what you want is to have a decent design for your site, but you can't afford or don't want to wait for a professional designer, buying templates is the best thing you can do. You can get a beautiful-looking template for as little as $10-$20 dollars, and they'll be much better than you could hope to accomplish with limited time.
Also, if you're looking to just throw up a website quickly, I'd look into getting it set up with WordPress + a commercial template. It will take you 3 hours to get a beautiful-looking website up on the net, and you can always copy the design (and the design's code) if you want to make a web-app with the same theme. This is what I use for all my sites - a quick WordPress site with a theme from WooThemes, and a web-app (sitting on a subdomain) with the same theme, copied from the original template.
Resources:
WooThemes - beautiful and very easy to use themes for WordPress (and a few other CMS', I believe). http://www.woothemes.com/
ThemeForest - also great themes, available for WordPress or as just plain html/css/js files you can play with. http://themeforest.net/
ThemeForest Admin Templates - I just learned about this one. ThemeForest templates, but that are specifically designed to serve as an "administration interface" for a webapp. In other words, if you're building a web application, these themes have everything you need. I haven't used one yet, but I'll definitely be buying a theme from here the next time I build a webapp. http://themeforest.net/category/site-templates/admin-templat...
Oh, by the way, if you're interested in learning Photoshop just for fun, I really recommend the Lynda videos - http://www.lynda.com/.