When it comes to learning any new technology, it's extremely tempting to take to Google, or even here on SF! However in my experience, the more I dig into the inner workings of different technologies, the more I value the good old fashioned book. Materials like O'Reilly guides are always a good bet, as well as vendor white papers and documentation, and ensure that you're getting accurate, up to date information. It took me a while to realize how important that is when you're first starting out with a new technology.
Forums and Google are another great starting point for expanding your knowledge once you have a good sense of the basics, and can help introduce you to new software, systems, and possibilities quickly.
Looking at other people's questions here on server fault is also an excellent way to learn about the intricacies of a particular system like IIS (check out that "Related" section to the right of this post). Reading about the mistakes and problems that others have had just might save hours of your time down the road.
And lastly, once you find yourself in a real jam, I haven't found any place better that SF as a place to pose intelligent, well thought out questions to a slew of experts and professionals with years in the industry.
Anyway, just my opinion as someone who has had to learn a lot new things quickly ;)