Furfly sponsored a port of ecommerce 3.x to the 4.x environment by ex-aD'er Walter McGinnis recently.
It's in our tree already and that will be our starting point, as the aD work wasn't even close to completion when the ax fell on the Tcl version. Also the existing OpenACS 3.x ecommerce port should be a useful reference for PL/SQL->PL/pgSQL porting, many or most functions can probably be used directly.
Civilution (ErikR and co-workers) are going to work on porting it, and Walter McGinnis is available to help with questions/issues regarding his earlier port effort (Walter's going to port the photo album stuff).
Ecommerce is a big package - why not e-mail Erik and see if they think they could use help in a productive way? They'll have two or three people working part-time on it so splitting it up further might not be practical, but it doesn't hurt to ask, right?
The plugins for alternatives to cybercash for settlment are interesting, I don't believe they're planning to do anything other than cybercash, so that's certainly an area where you could pitch in (mention it to them). Walter did pretty much a straight-across port so abstracting out the settlement process so we can plug various types in would be good. The fourth method folks with smaller businesses have expressed interest in is PGP-encoded e-mailing of orders for hand verification by the shipping organization. Folks who do low-volume mail-order are already used to doing stuff this way.