I would suggest to use REF191 as reference rather than PIC internal reference, as it more accurate. Consider quick calculation:- you have
10bit resolution ADC. In worst case you have to drop 2 bit LSB due to non-linearity, etc, this leave 8 bit accuarcy or 4V/256 = 15.6mV. or
1.56degC (assuming 10mV = 1degC). The resolution is 4V/1024 = 3.9mV or
0.39degC.
You can improve accuracy by setting to 0degC or 20degC (next to PT100), measure the readout and then calculate the error between calibrated temp sensor and the actual PIC readout. use the software to subtract the difference and the accuarcy is much improved. This process is calibration and take place after board assembly.