I didn’t look at your pic before spouting off. SPICE is not capable of handling microprocessors. Good for logic circuits and such though. What you probably want is the Virtual Arduino Breadboard.
Um, I don’t need a fancy analysis program to tell you if your circuit will work. It won’t. You will destroy your LED, because you have not included a current limiting resistor.
keep in mind that any electronics simulator is limited with respect to variances in components irl. meaning that if you are working with 5% resistors, there will be 5% variance between boards, and so also between your simulation and the board.
once you get the parts you are going to want a multimeter.