LINQ and QueryOver are completely different query methods, which are added to the ones that existed in NHibernate 2 (Criteria, HQL, SQL)
QueryOver is meant as a strongly-typed version of Criteria, and supports mostly the same constructs, which are NHibernate-specific.
LINQ is a "standard" query method, which means the client code can work on IQueryable without explicit references to NHibernate. It supports a different set of constructs; it would be hard to say if there are more or less than with QueryOver.
My suggestion is to learn all the supported query methods, as each use case is different and some work better with one, some work better with other.