I wrote this article for my friend Russell over at FanaticAttack. Lots of comments (I clearly need to do better at publicizing my own blog! ;> ). Check it out; it's definitely one of my more explicit, step-by-step guides.
Excerpt....
Here are some setup tips to help you get OpenOffice.org humming.
Automatic Settings
Some of the default settings aren’t quite what I would recommend, but it’s very easy to make the changes.
First, choose Tools > AutoCorrect.
In the Word Completion tab, turn off word completion if it bugs you
by unmarking the Enable Word Completion option. If you like it but want
to change what key you use to accept the suggestion, you can do that
too.

General Settings
A window you want to get to know: choose Tools > Options. I
strongly recommend that you go through every option in that window
since many are very useful. To get the options for text documents you
need to have a Writer document open first; to get the options for
spreadsheets you need a Calc document open first, and so on.
Printing
Writer printing: Tools > Options >
OpenOffice.org Writer, Print: you might want to turn off the option for
printing automatically inserted blank pages unless you’re heavy into
the first page of a new section starting on the right-hand page.
Calc printing: Tools > Options >
OpenOffice.org Calc, Print: it’s best to turn off both options here. If
you want to select two or more sheets to print when you’re ready to
print, just select one sheet tab, then hold down Ctrl and click on each
additional sheet you want to print.

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