Sony has finally taken steps to make their PlayStation Store more accessible to the masses. Those with a PlayStation login can now access the entire store online and purchase digital items and queue up downloads for both their PlayStation 3 and Vita systems.
Having played around with the online version a bit last night, I must say that it is a lot more accessible than the traditional versions. The stores on both systems seem to take a while to load the various links and to queu up items; however, on the web version it is as simple as clicking and then letting your console do the rest. If you have PlayStation Plus set up with automatic updates, then it should do all of the work itself over night.
Check out the following video for an idea of what you can expect: