There's a lot of great advice here and I'm not sure how much I can add. However a couple of things I haven't seen.
First, relax. Have fun. Make mistakes, and learn from them. All DMS (good ones anyway) know they can improve so don't be too hard on yourself.
Don't be afraid to limit some options, at least at first. For example, I decided a long time ago that Drow were the boogie man, so they're not allowed as an option. You don't need to allow feats or multi-classing right away if you don't want to.
Don't get too caught up in the rules during the game. With brand new people, I like to have an intro section where we just go over the basics - basically throw them into a simple fight and explain what their options are. That may include pulling out the books, reading up on things, making sure we all agree. After that? I usually just make a ruling during the game that makes sense to me and we worry about it after the game. See my first rule.
Being a DM is awesome. You get to paint a picture of a world, but remember that the players are there to help you shape that world. I remember an interview with an author that had started out as a D&D player. When they were asked if they still played they admitted that they did not because they always wanted to dictate the story and decide what the PCs should do. They realized that in order to be a good DM sometimes you need to let the PCs go so far off the rails you're not even sure what the original plan was, and that's okay.
I'm sure I could ramble on for a while. Things like get a random list of names for NPCs, shops and towns. There are a lot of tools online, I just use them to generate a list of names and then if I need an NPC on the spur of the moment I just grab one from the list. You can also get random descriptions. People are always amazed when I look up my "notes" that I had figured out ahead of time that they'd want to talk to the the baker's cousin and that his name was Josef who walks with a limp.
But remember the first rule. Relax, have fun, don't be afraid to make mistakes.
Good Luck!