If the throttle has 5V on the red and 0V on the black there should be a variable voltage on the white wire of between 0.8V and 4.5V as the throttle is operated.
As you have a reading of 0V on the signal wire (and assuming the throttle is OK) you either have a broken signal wire on the throttle side, or it must be short circuited to a ground wire somewhere on the harness side.
Check the voltage on all three wires on the throttle side of the connector, and then check the harness side to see if they are the same, any differences here would indicate a poor connection between the pins and sockets.
The motor should only run if the voltage on the White signal wire is above 1.25V.
If the motor runs fast, but stops as soon as you unplug the throttle, it could be that the white and black leads have somehow been connected the wrong way around.
It might also be worth checking for any damaged or shorted wires where the harness exits the Pie's axle, as the sides of the slot can be very sharp.
Alan