I realize that I am adding to this thread pretty late in the discussion, but I think some really good points are being made here and a couple I would like to add to.
While I paint in matte, I find that there are certain accoutrements that profit from a gloss finish, as a result, I use both acrylics and enamels. While I generally like the Vallejo acrylics and the color options, I find that most often (especially if you are painting may figures) it is much more cost effective to purchase large bottles of inexpensive acrylics from your local craft store. Vallejo paints are 17ml bottles, while I can pick up comparable quality 2 fl oz bottles for about $1 (and sometimes subtle pre-mixed shades unavailable from Vallejo). While you may wish to mix your own shades, the value of the premixed is that if you come back later to paint additional similar figures, the colors will match. Also...I write down precisely which paints I have used on each article for any given regiment for later reference.
I also use Testor's DullCote to protect the acrylics once most of the painting is complete, although I may complete some of the detailing with enamel following the DullCote. The enamels are generally durable enough not to require a protective coat, and if you DullCote after all the painting is complete, your gloss enamels will be as flat as your acrylics. For these gloss details I prefer Humbrol to everything I have tried; it is smooth and easy to apply and doesn't "glob" as some other brands do.
Regardless of the paints and techniques you choose to adopt, the most important equipment in your arsenal are your few valuable brushes. While I must have 20 or more brushes, I generally use the same five, beginning with a 15/0 (one 000 even cut down). Buy your brushes from an art store, not a craft shop. Get the best you can, and take very good care of them. You can use the same brushes for both acrylics and enamels, but be sure to wash them thoroughly after use. If you use thinner, wash the brush with soap and water after removing the paint completely with thinner. I still have every brush I have bought. The good ones will last a very long time if you don't "scrub" with them. I consider Floquil brushes adequate, my best being Kolinsky Sable brushes made by Winsor and Newton.
I don't consider myself a great figure painter, but I was surprised at how much better my results were once I was using the best materials.
That's my two cents.
Thanks.