Remote Desktop Protocol (RDP) is a proprietary protocol developed by Microsoft, which provides a user with a graphical interface to connect to another computer over a network connection. The user employs RDP client software for this purpose, while the other computer must run RDP server software (from here).
Launch CMD with other cretentials so they are used in the network
You can launch a new cmd to wich new credentials will be attached so, every interaction this new shell makes with the network will use the new credentials:
Session stealing
With Administrator rights you can access any opened RDP session by any user without need to know the password of the owner.
Get openned sessions:
Access to the selected session
Now you will be inside the selected RDP session and you will have impersonate a user using only Windows tools and features.
Important: When you access an active RDP sessions you will kickoff the user that was using it.
You could get passwords from the process dumping it, but this method is much faster and led you interact with the virtual desktops of the user (passwords in notepad without been saved in disk, other RDP sessions opened in other machines...)
Mimikatz
You could also use mimikatz to do this:
Sticky-keys & Utilman
Combining this technique with stickykeys or utilman you will be able to access a administrative CMD and any RDP session anytime