If you've installed OpenACS, all the documentation is available for perusing from by visiting /doc.
Several times per week, I use htDig to index the OpenACS doc (the bboards at openacs.org, the bug reports, and the wimpypoints), and you can get search that index by visiting http://theashergroup.com/demos/openacs.
Truly, the best way to learn about OpenACS development and architecture from scratch is to work through the first two problemsets in the online course http://philip.greenspun.com/teaching/old-one-term-web-6916 and then use these bulletin boards and other online resources for additional help.
Some of those resources:
- a tcl reference book http://www.arsdigita.com/books/tcl/,
- a sql reference book http://www.arsdigita.com/books/sql/,
- an AOLserver reference book http://www.aolserver.com/docs/tcldev/tcldev.htm
- an OpenACS 3.2.5 book http://www.arsdigita.com/doc/index-3.x.adp
- an OpenACS 4 book https://openacs.org/4/
- A wonderful overview of the ACS, it's development, and the philosophy behind it can be found in Philip and Alex's Guide to Web Publishing, http://www.arsdigita.com/books/panda/
You will have to take some of these references sources with a grain of salt, in particular the ArsDigita ACS 3 docs. It's really a very good introduction to the system architecture and development patterns, but the doc is for a system that is very similar to, but different from OpenACS 3.2.5
(Note to the webmaster: perhaps it's time for OpenACS to start mirroring the tcl/sql for web nerds books, panda, the problemsets, as well as the aD ACS 3.x books. )