To Open every character you need to collect a item in their chapter.

Mita

Open by default.

Cap-Wearing Mita

On top of the TV in the Kitchen in Beyond the World chapter. You can go to kitchen while Cap Mita is following you.

Tiny Mita

Appears after you meet Tiny Mita for the fourth time in The Loop chapter. It's next to her on top of the wardrobe.

Chibi Mita

Look at left of the Tiny Mita to see it on top of the table with a cactus plant no it. It's in the Mini Mita chapter.

Short-Haired Mita

On the table next to the mannequin that bites your hand. You get there in Mini Mita chapter after playing a game on the machine.

Mannequin Mita

Before going up the ladder look at the hand of one of mannequins in the water. It's in the Dummies and Forgotten Puzzles chapter where bunch of mannequins are following you.

Ghostly Mita

In Ghostly Mita's room next to a box on the cubbies. It's in the Dummies and Forgotten Puzzles chapter

Sleepy Mita

In bathroom on top of vent on the shelf in She Just Wants to Sleep chapter.

2D Mita

While talking with Mita in Novels chapter, you will be asked to go to Kitchen or Bedroom. Choose Kitchen and click on the 2D Mita profile device on the table in your left.

Mila

After Mila stops talking you can go to living room and find the Mila profile device on the table in front of TV. It's in the Reading Books, Destroying Glitches chapter.

Creepy Mita

In shadow of the fruit plate in the kitchen of the Old Version chapter.

Core Mita

Go to Core room in the Reboot chapter and select Advanced Functions and then Get Flash Drive.

Last Mita

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Collect all other achievements in the game and this will be obtained automatically.