PIC16F690 not working properly
There is so much messed up in the schematics, that it's pointless to read the words and delve into this more deeply.  Fix the obvious things first, then come back.



What voltage is Vdd supposed to be in the top left schematic?

What regulator is being used in the top left schematic?

Is that regulator really OK with just a electrolytic cap on the input?  It probably wants something with low ESR.  The electrolytic may be fine for bulk storage between power line cycles, but there should probably be a 10 &micro;F ceramic right in front of the regulator in addition.

The full wave bridge in the top right schematic is hooked up wrong.  It will short the AC every other half-cycle.  The transformer will get quite warm or the diodes will blow out.

I can't even begin to guess what you think D19 is supposed to accomplish.

24 VAC (assuming sine) full wave rectified is going to be more than 24 V DC, even accounting for two diode drops in a correctly connected full wave bridge.

You forgot to connect power to the PIC.  It's not going to run without power.  This really should be obvious.

A 1N4001 is not a good choice for the flyback catch diode for the relay coil, although it will probably work OK in this case if you don't try to turn the relay on again shortly after having turned it off.