With the old
GW paints, I would have suggested Regal Blue, but since they just redid their entire paint line, there is now a "Base" color appropriately called Kantor Blue.
The base(or foundation paints as they were called previously) are very user friendly in my experience. Thin the paint down a bit and do a few layers to get a good coverage.
If you have any experience at all with an airbrush, I personally prefer to do basecoating with that as it does a beautiful job and saves a lot of time.
On the
GW website, they've put up some painting guides, showing you the base, wash(shade), layer 1 and 2(highlights), etc. For the
CFs, go with the "Blue" guide, second on the left:
http://www.games-workshop.com/gws/catalog/paintChart.jsp?catId=cat820002a&rootCatGameStyle=
Although I was initially excited to hear about their new paint line, especially some expanded shades in purple and green, I've not been hearing very spectacular things about some of them.
I've helped some friends and family with learning how to paint in the past, and
imho, Privateer Press Paints are great for beginners because they provide great coverage, they have very strong pigments that you can thin down and still retain strong colors.
If you want to go that route, I would suggest Exile Blue for the base color, Cygnar Blue Base for the highlights, and adding Thamar Black to the Exile Blue for shading. For brighter stages of successive highlighting, add Menoth White Highlight and then Morrow White. For the red fists, I would go Skorne Red for the base, and then mix Skorne Red and Khador Red base 50/50 for the first highlight and then just Khador Red Base for the second.