I suspect you want:
var sorted = meetings.OrderByDescending(m => m.ActualStartDate ?? m.StartDate);
Note that calling the method won't change meetings
- you need to use the return value which will be a sorted sequence of results. (This is in line with how LINQ works in general.)
If that still doesn't work, and assuming this is LINQ to SQL or something similar, you should look at the generated SQL to work out what's going on... then you can try to adjust your query appropriately.