i think around 5pm like that shoot, dont need High ISO, just adjust ur WB. To maybe Sunny or Cloudy to have that kinda warm feeling. Just set Aperture to maybe lets say, F8. Depend on the lighting also, if its good, shoot around 5.6 to 8 or so. If u said the lighting its quite bright, why setting ISO at 800? Set to 100-200 will do. than the rest adjust ur shutter speed and Aperture will do. If u want to shoot both person, try shooting at F10 or F13, than Matrix metering. Aperture Prority mode? rather u use Aperture Prority mode than Manual since u are getting to explore with ur 40D. Yes, try set to JPEG.