I second what everyone else has said.
Ideally I want to boom from above and be inches above the talents head(rarely do I get this). Sound travels up. When you come from above you put the atmosphere/room and all the nonsense sound that comes with it, into the dead side of the shotgun. I aim for the solar plexis for a couple reasons, one is it gives me a bit more full sound in my opinion and two, it is much easier to aim for a larger target than the mouth, especially when your are using your peripheral vision many times. I generally am above the talents head and a bit in front of them to where the angle of attack is about 45 degrees, this allows for better flexibility for moving around and compensating for the unexpected.
Always try and swing the boom. If you just plop it between the 2 talent, then both are off axis. If you try and swing, they still may end up off axis, but you have a much greater chance of being on axis when you try and put them there :)
I think booming from below is a technique invented by camera or the ad, and I avoid it at all possibility.
As far as mic selection, that is highly situational, and depends on your budget. If you are just learning how to swing the boom, a mic with a wider pattern might help out because it increases your chances of putting them in the pattern. If you have a very tight pattern, being a couple inches off will make a huge difference.
Also be very aware of your surroundings. That goes for what is happening dialogue wise, where lights are, where you can be, and what is happening at the location. Make sure you LISTEN, turn off the AC units, Fridges, make sure G&E parked the grip truck an acceptable distance away, gels flapping in the wind. These problems are all easily adjusted when you do them while people are setting up and not once your rolling, nobody wants to work twice, many are willing to correct problems when you stop them before they get all set up. Many times I will take a portable pre like the little battery powered sound devices pre and just walk around with the headphones on and the mic, to pick out problems. It is also my experience that G&E crew are 1000x more willing to help you out than anyone in camera department. Making a movie is a team thing, so make sure you foster good relationships with someone in every department.
Booming is like a dance, ballet if you will. You have to move with the talent in the same time/space that they are and dodge every light and camera at the same time.
If you are also the recordist, aka one man band, learn to speak up when a situation happens. This is something that took me awhile to get over, but most of the time, you are the only one hearing what is happening, so you must have communication if something unacceptable happens in your opinion. If you are the boom op, most of the time you are also sound's communicator of problems, because your right there on set. Choose your battles wisely though.