Exhaust velocity is very important. You can actually get more scavenging by using an exhaust that creates high velocity. The reason for this is.... the higher the exhaust flow the more it pulls from the exhaust manifold, head, and cylinder. Mufflers slow this pull by creating preasure. Cats create even more preasure.
Would open exhaust be the best you can get, say comming out your headers? Well that depends on your target RPM range. On an economy box geared for an emphasis on milage only you need to focus on low rpm and this means high flow for less exhaust (low RPM). Smaller pipes are suited for higher pipe flow velocity and less volume. Bigger pipes are suited for higher pipe flow and higher volume. What this means is your pipes should be sized for your particular engine size, RPM range, and driving habits. If you like to rev out a bit and then drive the speed limit... maybe your looking for a slightly bigger pipe than stock like a 1/8th inch or 1/4 inch. If you like to drive for highest milage... Then the stock size is probably for you. If your a Street Strip driver than you may wish to go 1/2 a inch bigger or so. In any case a free flowing muffler and cat is what you should be shopping for. With a free flowing exhaust you almost always will get more noise. Best to go to some car shows and listen to what others are running to get an idea of what you would like your car to sound like.
I personally like flowmaster mufflers. They make a deep throaty sound and are quiet when cruising but get louder when your on the throttle. They make a pretty broad range of mufflers. Expensive though.
If working on a v6 or v8 it is a huge difference to run a couple of crossover pipes to share a couple of mufflers and cats. The crosover pipes should face towards the back of the ehaust and not be just a straight T from one pipe to the other.
Always trim the crossover pipe first then make the cuts into your exhisting pipes. That way you can fit them and locate them prior to fitting them. Also the crosover pipe
Should not protrude into the main ehaust pipe. The crossover pipe can also be much smaller than the main pipe as it won't be carrying full exhuast flow.
This is a example of a newer crossover design. It makes me go Hmmm.
http://members.aol.com/xforcefast/
This is an example of the worst crossover system involving a "H Pipe" Picture is about halway down
http://www.carcraft.com/techarticles/69238/
This is not very good as the direction of Exhaust flow has to make 90 degree direction changes and when it enters the main pipe next to it, it actually slows the outgoing velocity of the exhaust gases in that pipe.
This is an example of a "X Pipe" Design. It allows the gases to slam into one another but not nearly as bad as the "H Pipe" design. Flow master mufflers use this design to propogate noise reduction withing their mufflers.
http://www.torquetechexh.com/xpipe.htm
The dual crossover pipe design with crossover pipes set at 45 degrees between the two main pipes has long time been my favorite setup of mine. I cannot seem to find a good picture of that setup right now.
This is a pic of the wildest Header setup I have seen to date. It combines two headers to take advantage of the 90 degree pulses of the engine. A truly sweet setup.
http://www.thepowerbroker.net/scavenger.htm
Now for the single exhaust. You can use a y pipe towards the back of your exhaust to split it into two cats and two mufflers. This will maintain veloctity down your main pipe and then split the restriction of the cat and muffler into two cats and two mufflers. This should greatly reduce back pressure. Designing a good exhaust may be a bit tricky to get this type of system to work best.
Be aware that when you improve your exhaust flow you have to make adjustments on your fuel air flow mixture. Depending on the amount of improvement.... determins how much adjustment you may have to make!
Good Luck.