On some heads, the intake seat sits higher than the exhaust seats. You can mill a head down until you are getting close to the 45, then that is as far as you can go. In these cases, there is still material above the exhaust seats.
By milling on an angle ( taking more off the exhaust side or the head) you can get it down to where you get both seats at the same time. This gives you the smallest combustion chamber possible without welding.
Jay