It took me forever to learn how to do basic things like insert a XY chart in calc, just because the UI was confusing to me, and even after using it for a while I still keep forgetting which of the half dozen similarly styled icons I need to use to change the axis title of a chart, for example. Or the fact that to print off a spreadsheet in landscape, you don't do it through the print menu, you actually have to change the page formatting options.
I'm on version 6.0, so maybe this is fixed now, or maybe I'm just not very good at that kind of stuff, but it all seems pretty hard to use to me.