Looking to get into the hobby
I've had my first 65 gallon saltwater set up for about a month and a half. I had some trouble starting with my first few fish as they would not live for more than a day, but now I've got some chromis doing well.
Okay so first of all, the bigger the tank, the easier to keep the water quality in good parameters.
Secondly, you should cycle your tank using live rock. A good rule is one pound per gallon, but I went a little bit lower at 50 lbs for my 65 because it cost so much money (about $400 dollars, but I got a discount for $350 I believe)
Good fish to start with after cycling would be damsels or chromis, but keep in mind that damsels are very, very aggressive and chromis are peaceful to other fish, but can sometimes pick on each other.
Lastly, a good way to acclimate fish/inverts is a method called drip acclimating.