Baseline PIC12F509 BTFSS Instruction Issue
Well I figured it out and the answer was pretty silly.

As stated before I was powering this tiny circuit from the PICKit3 and my switch was on the disabled MCLR pin which when disabled becomes an input.

The answer is GP3 WAS being pulled low but not by me by the PICKit3. After programming the PICKIT momentarily pulls the MCLR line low to reset the microcontroller (the same line I was using for my input) for a split second. That logic low was enough to turn the LED on in my first bit of code and also toggled the LED on in my second bit of code.

The solution was to disconnect the PICKIT after programming and power the PIC from an external power supply. When powered externally the PIC code works as expected with the LED initially off. That'll teach me to treat the MCLR pin like any other input.