Which method is best to use for PS2 DVD's??

The Pioneer A03 DVR is the only sensible way. Burning tutorial on ####://www.psxcopyworld.co.uk .

Ripping will be increasingly difficult as games now reach 4.5GB and can't really be squeezed down to 650MB; going multi-CD is quite difficult, very time consuming and a steep learning curve as you've identified.

NEO2.2 chip will do or a Messiah clone if you can get it (much better than Neo2.2)