Right click to paint textures. There is a maximum number you can have per quarter cell (6, iirc).
http://www.creationkit.com/Landscape_Hotkeys
You can press "I" in landscaping mode while hovering cursor over a cell to see how many textures are currently being used. You can delete textures from the list to make room for more, but deleting the first texture in the list used to corrupt your cell. Not sure if that's still true.
Edit: Make sure you have the 'edit colors' box unchecked to paint textures.