If you make changes to the options in the printer dialog box and then print, the next time you print they will be reset to default. In particular I'm talking about duplexing. With OpenOffice 3.2 and before, it was possible to set the printer options on a document by document basis, and once you saved the document those would be the defaults for that document from then on. With 3.3 on, you can still save those settings, but they are ignored. If you go back to change the printer settings they will still be set correctly, but the print dialog will not use them. In addition, the print dialog does not even remember its own settings. If I print a document using duplex, then decide I need to print more copies, the next print job will be simplex unless I explicitly go back into properties and set duplex again.
I have a similar problem with landscape/portrait selection. I found 4 bug reports (33245, 33861, 36591, 37064) witch all seem to be a result of the printer-dialogue loosing it's settings, So I marked the last 3 as duplicates of the first one. Also, my problem seems to be fixed in the current Beta release (LibreOffice 3.4.0 DEV300m103 (Build:5) Windows XP 32-bit), so please check if this is still a problem in the latest beta release. *** This bug has been marked as a duplicate of bug 33245 ***