http://www.chemguide.co.uk/inorganic/transition/features.htmlTransition metal ions
You have already come across the fact that when the Periodic Table is being built, the 4s orbital is filled before the 3d orbitals. This is because in the empty atom, 4s orbitals have a lower energy than 3d orbitals.
However, once the electrons are actually in their orbitals, the energy order changes - and in all the chemistry of the transition elements, the 4s orbital behaves as the outermost, highest energy orbital.
The reversed order of the 3d and 4s orbitals only applies to building the atom up in the first place. In all other respects, you treat the 4s electrons as being the outer electrons.
Note: This is another of those things that you just have to accept. The explanation again lies well beyond the level you are working at. Just remember that once you have the full electronic structure for one of these atoms, the 4s electrons are the outermost electrons.
Remember this:
When d-block elements form ions, the 4s electrons are lost first.