Mmmm... I just got it working in WinUAE (latest version), although yesterday I did use my A1200.
I did this, in DefIcons add New type "xls" under "project", i.e. not in another MetaClass, look for PATTERN #?.xls
Save.
Opened SYS:Prefs/Env-Archive/Sys and from Wb menu "Copy"ed an existing icon (def_key). Did Icon Information and from there IconEdit, added crude X (!) to icon, saved. Renamed to "def_xls" (lowercase).
Now dragged an XLS file from Winbloat to my WinUAE HD "work" drawer. When I opened the work: partition in WinUAE and did Show All Files, it displayed the blank page default icon. Did F12->Misc->Reboot Amiga. Looked again, now picked up proper icon.
Have a look at
small grab of area.I do know that DefIcons is quite "clever" in how it matches. Yesterday I tested by making a quick test text file something.xls and DefIcons matched it first with ISASCII so it didn't get the xls icon but the "text file" one! So I tested then with a proper xls file.