You've got several questions in here:
Is it possible to use Sql Server XML columns as a substitute for a real Document DB (such as Couch or Mongo) ? Yes, you can use it as a substitute, but no, you probably wouldn't be satisfied with performance if you're exclusively storing XML and not leveraging any of SQL Server's relational tools.
If I were to create a table with a guid PK Id and an XML column for the document. What would be the main problems compared to using a document DB? In a nutshell, scaling out. SQL Server doesn't scale this kind of thing out well. You can do it with replication, but it's painful to manage relative to a "real" Document DB.
Sql Server supports indexing over XML columns so querying should not be completely horrible? The problem is that SQL Server's XML indexes can take several times the storage space of the original data. These indexes can't be maintained online (as in defrags), so you end up with locking issues during maintenance windows.