But why wouldn't you use a relational database? It works, the ORM's good, it's fast enough, you're probably not going to hit scaling problems. If you do hit scaling problems, then that's a really really good problem to have.
then incrementally add code as you need it, how/where you need it, including how to persist
But if I'm very confident it's going to become part of a long-lived dynamic web service with enough of the features Django provides anyway -- especially that awesome built-in admin UI -- then yes I start with Django. The mindshare/community factor is helpful too. I know there are other web frameworks which are decent but going with a big framework other than Django in the Python space today is a bit like going with FreeBSD rather than Linux when all you really need is some sort of free Unix. To pick Linux is to get a bigger ecosystem today and therefore probably also a longer supported future.