Main thing is the clock rates, increasing volts will able stability on higher clocks and so on. Your temp is good and if you are happy with performance no need to mess with volts.
There are a few options to play with in afterburner - core voltage, power limit, core clock and memory clock, while in catalyst there are only the last 3 options. What do they mean? Are moving them all up increase performance ( I took memory +core clock to the limit, played Borderland, temp was 60 max so I guess these 2 are ok.) .Should I monitor the motherboard too ? BTW I'm using a 19" screen, are these setting are overkill for such a (relatively) small screen ?
MSI afterburner has all the functions to monitor everything and OC the card. I use coretemp on all my rigs just to monitor. GPU-z is another popular one.