There are no special procedures for selecting the assist mode. You can switch from the highest assistance level to the lowest one (or even to Off) whenever you need. The opposite is also valid. You should only make these considerations:
Most of reasonable riders start in the lowest assist mode to conserve the battery charge. When there's significant headwind, the next assist level is chosen; when there is a steep hill ahead, the highest assistance level may be chosen. When riding downhill, many e-cyclists switch the assist off.
However, it is very important to operate the derailleur properly. At any given assistance mode, one should choose such gear ratio as to maintain the preferred cadence. Spinning the crank too slowly (mashing) is bad on your knees and on the battery.
So there are no rules how to "shift" assistance levels but there are rules how to shift the gears. In case of your Pinarello (rear-hub-motor) you just set the assistance level that is comfortable for you and you shift the gears to be at a comfortable cadence.
No more, no less.