Yes, this can be done, although the syntax is a little unintuitive:
trait Foo { def getInt: Int }
val fooStub = stub[Foo]
(fooStub.getInt _).when().returns(1).noMoreThanOnce()
(fooStub.getInt _).when().returns(2).noMoreThanOnce()
(fooStub.getInt _).when().returns(3)
(fooStub.getInt _).when().returns(4)
assert(fooStub.getInt == 1)
assert(fooStub.getInt == 2)
assert(fooStub.getInt == 3)
// Note that it's fine that we don't call it a fourth time - calls are not verified.
It's important to use .noMoreThanOnce() rather than.once(), otherwise you cause the calls to be verified. There is also a .noMoreThanTwice() method, but I don't think there is a .noMoreThanNTimes() or any equivalent.
Here is how to do "first time return X, and then always return Y" for mocks and stubs:
trait Bar { def getString: String }
val barMock = mock[Bar]
(barMock.getString _).expects().returning("X")
(barMock.getString _).expects().returning("Y").anyNumberOfTimes()
assert(barMock.getString == "X")
assert(barMock.getString == "Y")
assert(barMock.getString == "Y")
val barStub = stub[Bar]
(barStub.getString _).when().returns("x").noMoreThanOnce()
(barStub.getString _).when().returns("y")
assert(barStub.getString == "x")
assert(barStub.getString == "y")
assert(barStub.getString == "y")