This method utilizes the feature of Big Picture mode. You will be required to launch it multiple times, so beware of that. As well, you must have logged into both accounts at least once, remembering to checkmark "remember this user" when signing in.

First, you'll need to launch Steam in big picture. To do this, go to your settings>big picture.


































Once you've done that, Steam will relaunch, and you'll be at the Big Picture homescreen. From here, click on the power icon (top furthest to the right) and choose log out user.










After that, steam will restart, and you'll be at a new login screen where you can chose the user.










Upon chosing the user, you will be logged in, and will not require a password.










From there, you can go back to the power icon, and click exit big picture to return to the desktop mode.






And that's it!

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