Don't forget to offer PLENTY of immediately usable examples of the API. Like Pivotaltracker has copy/paste-able curl commands to try out the API. Have libs with consistent examples for all popular (and, if for some free PR, less popular languages). Version your API in the URL; you might need large changes to existing stuff, so you cannot trust on backward compatibility all the time while it is really annoying for devs when something works if they have to change it (or it stops working).

Edit; hire 'average' programmers from oDesk etc to build 'stuff' against it 'for clients' (threat it as a serious project) to figure out how easy it REALLY is to make things with it. Average programmers are, well, the average, so they will be the most likely consumers of your API. If they have no clue at all, you didn't go far enough perfecting everything. For instance we hired a bunch of devs to do a Windows plugin for our monitoring system and we found out our documentation and examples were completely unusable for them. We'll have to rewrite/refactor all of that and have them re-try.