Solution 1:

I know that EF Code First Migrations is relatively new tool but don't forget about you are still in .NET.

So you can use:

if (System.Diagnostics.Debugger.IsAttached == false)
{
    System.Diagnostics.Debugger.Launch();
}

After that you can see your InnerException.

Or you can use try...catch statement like this: Exception handling Entity Framework

Solution 2:

To hit a break point in a db migration set the context to MigrateDatabaseToLatestVersion on initialise.

Database.SetInitializer(new MigrateDatabaseToLatestVersion<EnterContextHere, Configuration>());

Then you just debug as normal (run using f5) and the breakpoint will hit the first time you run the project.

The problem now is that if you debug a second time the migration will not run. This is because the __MigrationHistory table has been updated to say you have migrated to the latest version. To re-test the migration open the package manager console and downgrade to the previous migration:

Update-Database –TargetMigration: ThePreviousMigrationName