So basically your flash is roughly daylight balance (in experience I've always felt it a little cooler), the sunset is a nice rich warm amber, hence the term "golden hour". I don't have an example handy right now, but an hour earlier and I could've stepped outside and show you, but basically, the flash looks blue while the natural light looks orange, in Raw, one or the other is fine, but when you start mixing them it looks obvious that you used flash, so the blend is gone and it's obvious that you're manipulating the light, with all these blue faces and gold surroundings. Put a filter on your flash to match the color temperature of the ambient, and now you're one step closer to achieving the blend, and when you adjust the white balance in post, it's all matching so you're not required to use LR4/CS5 or later, and a series of brush adjustments, you just need to grab the WB slider and fine tune.
I'm trying right now to dig up an Adorama, Joe McNally explanation, as one of his videos was the first time it was explained in a manner that it all clicked for me.
These aren't them, same concept, though a bit Nikon specific.
https://www.youtube.com/watch?v=ntoRpQCY60U
https://www.youtube.com/watch?v=W3azZ0wIXpo
Ok you've got some modifiers and can get the flash off camera, that's going to be huge; and it sounds like you're planning to use the strobe as a key light. I'd probably put the flash off to a side and start with the 45/45 (up/to the side), and perhaps if I could prop it up, use a reflector (white/silver/gold depending on the color of the light) low and to the other side to soften the shadows a little more or help boost the front light if the sun happens to be a bit strong.
Shutter dictates the ambient, aperture dictates the flash strength and the DOF, ISO will help the camera be more sensitive to the flash, and closer proximity will make the flash brighter and soften shadows.
If you decide to go manual, I've heard a good starting point is 1/125 f5.6 ISO 100; though that's more where I start when working flash only, I'd probably take an ambient, start the flash at half power dial it up or down until it looks even (so for example if your flash goes 1/1-1/32 start at 1/16 too bright go 1/24 too dark go 1/8, then move in that same split the difference until it's where I want it), adjust the color, add the reflector as a subtle fill; pose everyone and snap away. If you've got a friend that's willing to pose or even a basketball you can practice during the week.