I'll strongly second that reccomendation for illustrator. Not only can you "save for web" from illustrator in exactly the same way as Photoshop, but you can be 100% certain that no matter what size you decide to publish your vector image at, it will be the cleanest and sharpest it ever can be. No messy interpolation blur. Lest us not forget Illustrator's all-too-recent interaction with Flash - exporting graphics in swf format for later Flash importation has cut my work time in half. As for style - well, it's more than just the tools you use. You do have to look, choose and learn what's out there, but I can assure you that, no matter how much you read about it, your first hands-on experimentation will seem as trial and error until you find a palette of styles/tools that are "yours". You'll learn to do drop shadows, then you'll pass a period overusing them - each new technique learned will 'fade into' the last, and eventually you will have quite a few to choose from. This takes time.
The best approach to learning anything is to have a goal first - for a real project or job. Decide what you want to do, how you would like it to look (I'm a pen and paper guy for this), then go about learning how to do it. You will feel more comfortable much faster with your new knowledge once you see the end result working in front of you.
And yes there is the education part - you have to learn at once the language of how images "talk" to people (what people recognise in them) and use that language to create a message, for your client, that talks to the audience he wants in the way he wants. This of course calls for a panopoly of styles, so as said earlier, having just one "look" will in the end just work against you.
I've rambled long enough - hope I added something helpful.
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