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By default Windows 8 will show you the main account when you boot up but that's not helpful when you have multiple users. Here's how to change the user account on Windows 8 start up.
If you remember the good old days of Windows 7 and being able to have the whole family lined up on the log in screen, everyone with their own user account, then you might be a bit annoyed with the way Windows 8 works.
When you boot up a Windows 8 laptop or PC, you'll see a lock screen which need to be moved with before you can log into your account. It will only show the main account here unless you click the back button (left pointing arrow) next to your account profile picture (see above).
While that might be frustrating, it's the easiest way to view all the available accounts. However, there is something you can do to change this. In the user accounts section of the control panel you can force the old-school Ctrl+Alt+Delete method for sign in which when done on the lock screen will take you through to all the accounts.

How to change the user account on Windows 8 start up

Step One
On an admin account, open the control panel. This is accessed by the settings section of the Charms bar.

Step Two
Click on User Accounts in the list.

Step Three
Click 'Manage User Accounts'.

Step Four
Click the 'Advanced' tab at the top of the window.

Step Five
Tick the box in the 'Secure sign-in' box at the bottom and click 'OK'.

Here's what you'll see after the changes