Spaces - how to set apps to appear in assigned desktop

Wrapping my brain around how Spaces work in Mavericks.

I have set a new desktop Space for individual app and some Space with a group of apps and wish it can open to those specified Spaces on every start up.

However it seems it isn't doing that.

I have switched off "Automatically rearrange Spaces based on most recent use"

I feel I am using Spaces incorrectly? 😝 Can someone help me out?