Well, I love Polly Scale, but it's been discontinued—by Testors. They bought the line, changed the formulation around 2007, and dumped it in 2009. Still available from stocks, but quality has slumped. Their railroad line is still in production, but you'll have trouble with color matching to A/N or FS standards.
Tamiya makes great paint. Some have trouble brushing it (requires special technique). Gunze Sanyo is similar but even more expensive, but is supposed to be easier to brush paint.
I've heard great things about Vallejo, but have only tried it in small amounts. Very fine pigment. Their Model Air line is for airbrushing, Model Color for brush painting.
MisterKit is odd stuff. Doesn't brush well, but airbrushes nicely. Cured paint is somewhat brittle, resistant to alcohol and Windex, but attacked by mineral spirits, so it has to be coated with Future before you use an oil wash.
I've heard good things about Xtracrylics, but not tried them yet.