Hi Adrian, ofcause 4S is much better, you can check with GWS website, then u know why....
http://www.gws.com.tw/chinese/product/powersystem/edf64.htm pls scroll down to see the data, on 3s, you only draw 10amp each motor, and only produce 300grams of thrust, but if you put 4S it only draw 16amp, but your got 500grams thrust, so it about 40% more push for your baby, but ofcause it won't be fast like hell, but atleast you got confidence to fly it, as you got more power, right?
But for the ESC case, i have no idea, don't thing if only connect to 1 esc it will run2 motor, unless something wrong.....

if you looking for cheap and good quality battery, look for loong Max, you can buy 2S 2250mah X2 so to make it 4S. now i change all my batt to this...

and it still work great!