If you have administrative access to a workstation on which the target user will log on, you can use the aforementioned Windows Credentials Editor to steal the plaintext password, at least on Windows 7. (Windows 8 seems to have disabled the Digest Authentication module that leaks the password.) You'll probably need to disable or add an exception to the antivirus software, or alternatively use a PE packer - WCE is regarded in some places as a hacking tool. (Makes sense.)
Using your form of admin power, be it local or domain (use the ADMIN$ or C$ share), drop the WCE executable and a batch file containing the following somewhere on the target computer:
wce -w > pwd.txt
Open MMC and add the Task Scheduler snap-in pointed at the target computer. Add a scheduled task with the following settings:
- General tab
 - Click "Change User or Group" and select SYSTEM
 - Check "Run with highest privileges"
 - Check "Hidden" if you want to be extra sneaky
 - Triggers tab
 - Add a new trigger
 - Pull down "Begin the task" and choose "At log on"
 - Choose "Specific user", then "Change User" specifying the target account
 - Actions tab
 - Add a new action
 - Ensure "Start a program" is selected
 - "Browse" to select the batch file
 - Conditions tab
 - Uncheck "Start the task only if the computer is on AC power"
 - Settings tab
 - Uncheck "Allow task to be run on demand"
 - Uncheck "If the running task does not end when requested, force it to stop"
 
EDIT (11/25): Alternatively, you can use PsExec to grab it from an existing session immediately and silently. See the new post.
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