ref~ is shorthand for ref~1 and means the commit's first parent. ref~2 means the commit's first parent's first parent. ref~3 means the commit's first parent's first parent's first parent. And so on.

ref^ is shorthand for ref^1 and means the commit's first parent. But where the two differ is that ref^2 means the commit's second parent (remember, commits can have two parents when they are a merge).