Hi João,
I am assuming that your 300 Ohm resistor and LED are in series, attached at one end to 3V3 and the other to the reset (RESET_b) pin line which has the button to ground.
Looking at the datasheet, I suspect the problem is with the voltage across the LED which brings the voltage at RESET_b to below the Vaio+Vhysh (This is the reset low level and power up hysteresis value) but *above* Vaio+Vhysl (reset low level and low voltage hysteresis value). This would mean that the processor is held in reset during power up, but would execute after you press the reset button - there is a 20mV differenced between Vhysh & Vhysl.
The best solution is to remove the 300Ohm and LED from the circuit and replace them with a 100k pull up resistor (I recommend 100k so that you can work with debuggers and the 100k won't interfere with their operation) and, if you still want to have an LED indication that the board is reset, use a FET buffer to drive the LED.
I suspect that you're using a green/blue LED which has a high forwards voltage, you might want to try an LED with a lower forward voltage (like a red one) and see if that fixes your problem (and validates my hypothesis of what your problem is).
Good luck and let me know how you make out.