My personal opinion is 5e is where to start for many reasons...
1. The simple, bare bones rules are available for free, so you can decide if you like it before you start buying a bunch of supplements and what not.
http://dnd.wizards.com/articles/features/basicrules
2. The rules are WAY simpler than 3.5, the character classes are far better balanced (though there are still many holes/loopholes, etc.) Now, regardless if you go 3.5 or 5e in a tabletop setting you do have the benefit of just disallowing game breaking stuff, there is far less you have to worry about in 5e.
3. If no one has ever played before, the leveling process/character creation/etc. is also much easier to follow... There is no more BAB and AC getting to the 60's, the numbers stay low throughout and thus are far easier to manage without needing a calculator in your sessions.
No expert as I only played 3.5 PnP for a couple of sessions maybe 15 years ago and have only DMd maybe half a dozen sessions and been a player in 3 sessions for 5e over the past year and a half. However, IMHO 5e is really a lot more fun to role play with buddies around a table. There is far less time spent looking up rules, calculating bonuses, etc. It's just easier to play when you aren't a computer. Game speed is a thing with sitting around a table because if you are only going to play every other week for a few hours considerations need to be made for how much you can actually get through story wise. If you spend an hour and a half on every encounter due to needing to look up all the various rules for abilities, classes, etc. you won't get much done.