Inaccurate and non-precise voltage reading from Arduino Analog pin
This should be a lot of fun but you might consider doing some research on analog circuits and A/D circuits. You have way too many digits to the right of the decimal, the accuracy is not there. The best you can get is 0.0044 volts per count with a 4.6v reference. What are you using to make your measurements, you need at 5 1/2 digit meter to have the decade better accuracy then what you are calibrating to. Your reference you state is 4.6 volts, something is not correct is should be 5.000V. You know any load placed on the on board regulator will have an effect on your A/D readings. The tolerance of the resistors you are using will have an impact on your reading. They generate noise that could be affecting your readings. 100nF should be enough capacitance,this will lower the input impedance. Increasing capacitance beyond this will slow the settling time of the circuit. If you are powering this from a computer USB expect noise from that power source, That would also explain the lower reference voltage on the A/D. With what you indicate you have, you are actually doing very well.