This is not correct. First, let me explain the following:
Clicking the "sign out" link in the browser signs you out of the browser session, not the client session. If you are interested in terminating the server connection when editing an online document from within Office, please close the Office client.
Now, if there is a case that the user is still authenticated in subsequent attempts it is because the user had selected "remember my password" at some point in the past on the Windows LiveID dialog. Please use the Office Live Add-in to "Sign in as another user" to eliminate this.