Painting
Painting minis is where I started miniature wargames. I actually had a painted WH40K v1 army before I knew it was for a game and due to this I always try to play with painted armies.
I measure painting techniques by two parameters: The quality of the finished result and the speed of which it was achieved.
I paint to play, not to win prices. I'll rather have a fully painted army of medium quality painted miniatures than and unpainted army with a brilliant painted general.
That is why I mostly prime my miniatures black, it adds a natural shade straight away, so it is just a matter of highlighting up. Priming miniatures black also give them a more solid and dirty feel of somebody in battle.
Having said that I do prime some miniatures white. For example Bilbo was painted primed white because he is not really a soldier and not on adventure anymore.
Also my Forsaken miniatures are all primed white because I wanted a really shiny warband (and a Forsaken army don't require that many miniatures so I feel I can afford giving each some extra hours).
Paint
Although I have only recently learned about Coat D'arms paint, I can already say they are some of the best paints I have ever used.
As far as I know Coat D'arms was the paint formely used by Games Workshop before they changed supplyer (and lid).
Anyway I first heard about Coat D'arms from artemis Black where I also bought the Dark Age minis I have.
Coat D'arms paints are just brilliant. It is a pure pleasure using them after being stuck with the half dried up Games Workshop paints. Coat D'arms are more liquid than I remember the old GW paints but that is find by me as long as they are still solid colour which they are. Of course you cannot cover black with yellow in one go, no paints are that solid, but you get the point. I can only give my highest recommendation of Coat D'arms colours.
Note I cannot recommend using Coat D'arms undercoat spray!
I bought a white one to try it out. First of all it is a can half the size of a GW primer. Second of all it is very thin.
No matter how hard I shook it it was still thin. So I had to give the miniatures coat upon coat upon coat... I was doing 6 minis and I'm just glad I wasn't priming a whole army.
By the time the can ran out they still weren't properly white yet.
In the UK you can get Coat D'arms from www.artemisblacks.com were you can also see a colour chart.
Brushes
One tip: Go to an art shop and buy some brushes there. They tend to be both better and cheaper than your average gaming brush.