Hi
In ZBrush 3.5R3 usage of multiple CPU cores is most likely already enabled. As far as I know Preferences > Performance > MultiDraw is the only switch you need enabled to take advantage of multiple CPUs. In my experience Preferences > Performance > MultiThreaded Steps should be left at 6. Lower than that will decrease performance, as will anything higher than 7. But feel free to experiment.
As for memory settings I would leave them at the default especially the Undo setting. ZBrush will always try to reserve as many undos as there is available memory to do so. A higher value will just force the program to store undos when you are running low on resources for other functions.
As you have a 64 bit OS and 8 Gigs of ram you could increase Preferences > Performance > Compact Mem to the max of 4096 but the difference will be neglible, IMO, compared to previous version of ZBrush. The newer versions of ZBrush (3 and on) are intelligent enough to stop compacting memory to disk when the cursor is moved, in other words it only compacts during inactivity. Of course if ZBrush has to compact memory to perform the next operation it will do so regardless of your Compact Mem setting.
I prefer that Zbrush compacts memory fairly often ( the default ) so while I check a reference picture or browse the web it is more responsive when i return. Well that is how I look at it.
Preferences > Mem > MaxPolyPerMesh and HD Preview MaxPoly are settings I would only change when the need arises. For example if your MaxPolyPerMesh say 20.5 (million polygons) and you need 23 to subdivide once more, then go for it and change the value. But remember to save beforehand 