Okay, I'll give it a go.
Nothing wrong with Coat D'Arms paints and the starter set seems a good place to, er.. start. From what you posted you might think also about the Goblin Set. Also remember you can use basic acrylic hobby paints which come in very large bottles very cheaply and I think you will find that most folks around here have tried and used them. Paint is one of your basic tools and eventually you will probably end up with hordes of bottles. I have at least 100+ bottles of paint.
As for brushes, I don't have any experience with em4, so I can't comment. I buy my brushes from the Evil Empire (GW). In general, however, the first thing you need is a really good point on a brush for detailing. Finding one, however, is not always easy. Many times I will buy say 3 fine detailing brushes from GW in hopes that one will have a nice point. Once you have a nice detailing brush, use it sparingly, only when you really have to... a really nice pointed brush is worth its weight in gold, so don't over use it. Besides a nicely pointed brush you should have a larger brush for block painting your base color. I also recommend a flat dry brush and a very large, soft brush for "cleaning" your mini's prior to applying your varnish.
Overall, though, Rob's advice is right on. Painting is a skill and practice is what it is all about. Dive in, practice, practice, practice, don't be discouraged with your early results and try different techniques. Eventually you will find your own way of painting and then you will really be off.
Good luck!