You will not need to worry about DLL files since you are not running on Windows. Debian's aptitude (or apt-get) should configure everything exactly as you need it.
If you had to add "extension=pgsql.so" then it was not installed correctly. Are you trying to use PHP as CGI, CLI or an Apache module?
Assuming Apache module, you should see a file "/etc/php5/apache2/conf.d/
If that file is missing, try this and tell me what you get:
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by: webwyzsystemsPosted on 2009-04-09 at 09:42:30ID: 24109013
As well as uncommenting the line in php.ini you also need to copy php_pgsql.dll to somewhere in the PATH (example: c:\winnt\system32). The php_pgsql.dll DLL should be in your PHP installation somewhere, you'll have to search for it.
You shouldn't ever need to ADD anything to the php.ini file. It has everything generally needed. You only need to uncomment the appropriate lines.