If you're only checking one blob and you don't need to discover the upload URL, then they're equivalent.
The stat handler lets you stat multiple blobs in one HTTP request. In an all-SPDY world (soon, effectively, at least for Camlistore users) that could be replaced with hundreds of HEAD requests instead of 1 stat request. And then we could define a different means of discovering the uploadURL, or make it well-known per-server, like the other handlers. For legacy reasons, we made it dynamic, but those reasons (App Engine limitations) are gone.
So really the advantage is minimizing HTTP requests currently.
When discerning the presence of a blob within a given blob server, is it preferable to make a HEAD request and check to see if a 404 is returned or should a stat request be made? Both of these do the same thing (more or less), unless I'm missing something.