An Arduino output pin would connect to 1, 2 on ground
Yes, the Arduino would set the output pin to high, causing the LED to light up the phototransistor, causing current to flow thru the opto-isolator.
should I put a resistor?
Depends what the datasheet of the opto-isolator recommends as forward input current (the current thru the LED). If in doubt, treat it as any old LED and yes, put a resistor in series.
And on 3-4 is the 12v 500mA.
Not sure I understand what you mean by that, the idea is to use the opto-isolator to control the flow of current into the gate of the SCR while protecting the arduino side from any large voltages and/or current which occur on that side. The SCR should be set up to short two contacts on the hot-shoe when it goes conductive, and its gate or control input is the thing you want connected to the opto-isolator.
You could do what ericski's link (glacialwanderer.com) is suggesting here, and use the opto-isolator itself to short the flash contacts, but I believe that's a bit much for such a part and the SCR will serve you longer and better. Happily, the opto-isolator should fail without passing the damage on to Arduino in any case.
As for picking the opto-isolator, if you are using it with an SCR, it only needs to survive any nasty surprises coming out the SCR gate, so the SCR datasheet will tell you the minimum ratings you need. The one you pointed to should be fine, but do check with the SCR ratings.
If you are using the opto-isolator to short the flash hotshoe directly like glacialwanderer.com seems to be doing, you need something beefy that will stand a few hundred volts. Glacial wanderer's opto-isolator's datasheet seems to suggest the PS2532 is a rather macho part. The collector to emitter voltage is 300V and the isolation voltage is 5,000V, compared to 30V and 5,000V for the part you pointed to.
The collector and emitter are the bits which will connect the gate of the SCR to ground or the two flash contacts together (shudder) so for the latter, 300V is a good thing while for the former, 30V might be enough depending on the SCR. The isolation voltage is how much voltage can be applied to the flash side of the isolator without making it to the arduino side, so either part, at 5,000 volts, should be fine for protecting your I/O pins.