Thanks
@Phil V for the mention.
Mid tone grey is yr best starting point. Watch any online tutorial by any of the best photographers who do this, it tends to be grey.
By the way although you can automate the masking process to a certain extent, the only true way to mask properly is by hand. If u haven't got one already, you'll need a tablet.
EDIT: Typed this while on my phone sitting down in a small room if you get my drift.....

On main PC now.
If you are shooting fast whilst running a studio at an event, where you haven't got time to edit then green screen is great using the proper software to just drop the person into a logo'd background for quick print. The green works well, but if you need to be approaching something like pixel perfect or need hair to be masked properly then it isn't the way forward.
If you are looking to do composites where you want to extract a person from a photo and place them in a separate background where your mask needs to bear better inspection then shoot against grey. Why grey? Why not another colour? Well as mentioned either here or in another thread, if you use a colour it will invoke a colour cast on to the subject which you wont want for your final composite and can be a pain to edit out. I've also shot against unlit white or black where I know the end image would either be high or low key accordingly.
As for the processing after you have completed the mask, you have to consider from subject to background the perspective, focal length, light direction, light temp, shadows, interaction, composition, to name some. Plus even when you have got everything right the subject can still sometimes just look 'stuck on' to the background, that's when some of the little tricks and tips you have built up to blend come in.
Composites can be simple such as just changing the background to a different colour, or complex where you want to make a full on action image with crazy explosions and space ships and stuff. If you don't get all these elements right it just looks like poop. I've seen green screens of a corporate shoot where although the subject was masked well, because the perspective wasn't right it looks like they are sat on the floor or have no legs. I've seen crazy full on scenes where focal length and depth of field have just been ignored. If you are going to paint on blur (which is a common tool in composites to create depth of field), you have to do it properly, or it may end up on one of these photoshop fail websites.
I've made a lot of these mistakes in the past learning to complete composites but that's part of the fun of a good development path, and the right attitude is to always know that there is always something new to learn. It's a journey of hard work and sometimes a lot of swearing to be good at these, but an enjoyable one.
Examples of a lot of my comp work here.....
http://www.charterphotography.co.uk/portfolio/digital-art-photography/