How can I group Vertices for easy painting I am starting to paint my character with few basic colours, but there are multiple vertices throughout my mesh, is there a way to assign groups to specific vertices of that mesh, for when selected I can easily apply a material. Thanks!
Yes, its possible!

In Edit Mode, select the vertices. In the Object Data panel create a Vertex Group, name it what you want and hit Assign.



Now, in the 3D view menu, Tab back into Paint Mode and toggle Face Selection Masking for Painting . You will notice the masked areas are now grayed and can't be painted.