I think in a lot of cases its not even the advanced stuff that keeps people on Excel and other proprietary things. It's the seemingly little things.
My biggest beef with LibreOffice's spreadsheet (and with Apple's Numbers) is how they handle copy/paste of discontiguous selections.
Consider this 5 row by 3 column set of data:
1 2 3
4 5 6
7 8 9
a b c
d e f
Suppose you select the 1 2 3 row, the 7 8 9 row, and the a b c row, copy them, and paste just below the d e f row. In Excel you get this (first 4 rows omitted for brevity):
d e f
1 2 3
7 8 9
a b c
In LibreOffice and Numbers you get this (empty cells denoted by "-"):
d e f
1 2 3
- - -
7 8 9
a b c
I haven't found a setting to change this. Excel doesn't have a setting for this either as far as I know, so people who do want discontiguous copy/paste to preserve spacing would probably be as irked by Excel as I am by LibreOffice and Numbers. But I don't think I've ever actually wanted the spacing preserved so it is LibreOffice and Numbers that irk me.