You have conflicting requirements so a compromise has to be made.
Yes, a Zener diode across the ADC input is the simplest solution and as a bonus, it will protect against negative voltages which could damage the ADC.
The conflict comes from the need to protect the amplifier as well. A 4.7V Zener shold hold the ADC voltage below the 5V VDD and still give you most measurement range but it will also sink op-amp current if it tries to go over 4.7V at it's output. The cure, is to fit a current limiting resistor in series with the op-amp output but this also introduces side effects, one is to limit the ADC input current so you may have to wait slightly longer before measuring if you are switching between other ADC channels, the other is it will create distortion in the highest measurments as the Zener starts to conduct. A Zener doesn't have a perfect knee point, it starts to conduct just before it's rated voltage and continues to conduct more to just past it. It means as you approach 4.7V some extra voltage will be dropped in the resistor and make the reading slightly lower than it should be. This effect will only happen near to 4.7V though so it may not cause you a problem.
Another option is to keep the series resistor but instead of a Zener diode, use two normal diodes, one to ground and one to VDD. Connect both with cathode ends toward VDD. These will conduct if the voltage goes Vf above VDD or Vf below VSS wher Vf is the diode forward voltage drop. Technically, this puts the range outside of safe limits but if you use Schottky diodes or types with low Vf it should be OK. For example a BAT85 diode has a Vf of around 0.3V compared with a normal 1N4148 type which is around 0.6V.
Brian.