var q = from c in metaData.Customer
where c.Orders.Count()==0
select c;
there are other alternatives, with .Any as well.
also, your query with:
var q = from c in metaData.Customer
join o in metaData.Order on c.CustomerId equals o.CustomerId into orders
from order in orders.DefaultIfEmpty()
where order.OrderId == null
select c);
should work too (although I haven't tested that last query).