Aside from my HTTP/REST rant, I think there's a much better discerning factor between POST and PUT. From the HTTP spec:
"The fundamental difference between the POST and PUT requests is reflected in the different meaning of the Request-URI. The URI in a POST request identifies the resource that will handle the enclosed entity. [...] In contrast, the URI in a PUT request identifies the entity enclosed with the request -- the user agent knows what URI is intended and the server MUST NOT attempt to apply the request to some other resource. If the server desires that the request be applied to a different URI, it MUST send a 301 (Moved Permanently) response; the user agent MAY then make its own decision regarding whether or not to redirect the request."
So if you want to create the user Foo and you somehow know about the URI example.com/users/Foo, then you can directly PUT your information to that URI. This URI points directly to the enclosed entity, the user. If you only know the URI of the enclosing resource (aka collection), then you MUST do a POST to example.com/users/.
So that's the semantics of it, PUT deals directly with the resource that the URI points to, while POST deals with a collection of subordinate resources.
However, the REST catch is that if you follow the HATEOAS principle, there's (almost+) no way you would know about example.com/users/Foo. In the REST world, you would (almost) never use PUT for creating, because if that resource doesn't already exist, you would (almost) never get a URI to it by traversing the hypertext representation of the application state.
+ I say almost because you could have something like a GET example.com/users?name=Foo that would return 404 with the URL where to PUT to create this user. Not sure how HATEOAS proposes you get to a URL like example.com/users?name=Foo though, perhaps someone more knowledgeable can pitch in.