For a web application that doesn't have an existing large user base, functionality is definitely more important than scalability at the beginning. It's not that you shouldn't use best practices that also help scalability -- it's just that you shouldn't make exceptions to some best practices because they hurt scalability. You can just concentrate on correctness and proper programming, then if your app begins to show issues with scalability, you can fix these as necessary.
Now if you're Google, and your coming out with Gmail or Google Maps, I think scalability should be a top priority from the start. If you're almost positive sure that millions of people are going to use it, you should design (and definitely test) with that in mind.