One thing companies with serious scaling problems will do is send you to places like e.g. JavaOne (and many, many more specialized conferences besides), where in the presentations you'll listen to e.g. LinkedIn talk about how to make writes immediately consistent to the originating user and then fan them out to other users over the course of the next few minutes, and what this requirement does to a three-tier architecture.
There's also a lot online. High Scalability will get mentioned, and I tend to keep my ears to the ground for interesting conferences and then see if they post videos and/or slide decks (SlideShare is wonderful for these).
OK, that's the answer you want. Here's the answer you need: you are overwhelmingly unlikely to have scaling problems. Single servers are big-n-beefy things, even single VPSes. Depending on what you're doing with it, a single EC2 instance running a non-optimized LAMP stack can easily get you to hundreds of thousands of users served, and/or millions of dollars of revenue. The questions of a) where do I get hundreds of thousands of users? or b) how do I convince businesses to pay $100k a month for my software? are of much more immediate and pressing concern to you than how you would take that very successful business to 10x or 100x its hypothetical size.
(Much like "I'm concerned my experience with managing a household budget will not prepare me for the challenges posed by a 9 figure bank account after I exit. How will I ever cope? Where can I learn about the tax challenges and portfolio allocation strategies of the newly wealthy?" the obvious answer sounds like "You'll hire someone to do that for you. Now, get closer to exiting than 'Having no product and no users' and worry about being a hundred-millionaire some other day.")