Congratulations on your new equipment. I would say you made a very good selection.
I'll second the suggestion that you shoot RAW and I'll also second the suggestion that you set a Custom WB with your camera.
By setting a Custom WB the internally generated JPG that shows up on the camera LCD will have correct colors. You should never base the WB setting (or exposure) on the camera LCD, it just isn't accurate enough, but having the image look as correct as possible makes judging the composition of your images easier since it removes distractions.
Programs like Lightroom will also look at the camera WB setting and open up the RAW image with that WB selected. Of course you can then change the White Balance and Tint if you want but at least you are starting at a standard point.
If you have a flash meter learn how to use it and be sure to calibrate it to give you accurate exposures. With RAW files the best exposure is usually about 1/3 to 2/3 stops higher than what a flash meter will read straight out of the box because of the greater dynamic range of RAW files.
I calibrated my flash meter by using a white target and the HA-ETTR technique. I used the 81% and 96% white squares of a GretagMacbeth Color Checker Target but a sheet of white printer paper will do since its reflectivity is about 95%..
With the camera Highlight Alert turned on the best RAW exposure was about 1/3 stop greater than when the white printer paper target just started to blink. With JPGs the best exposure was just before the white target started to blink and that was about 1/2 to 2/3 stop less exposure than for RAW.
When I open my images in LR4 I find that they need little or no adjustment of exposure but I usually adjust the Blacks slider a small amount to give me some richer shadows with just a trace of pure black in them.
Living and loving it in Bangkok, Thailand. Canon 7D - See the gear list for the rest.