Should  be a SELECT INTO and look something like:

SELECT Admin2.Name, Admin2.Number
INTO AdminNew
FROM Admin2;

Assumption is that you are getting a syntax error.  You really need to tell
us what error messages you are getting rather than "Access does not like my
code".

Missing a space between tblRptFreeSpotList and the list of fields
Missing a space between the list of fields and SELECT
Missing a space between MasterList and WHERE
Missing a space before ORDER BY  (by the way, the ORDER BY is probably
useless in an insert query)

   Dim Num As Long, StrSQL as String
   Num = 2

   StrSQL = "INSERT INTO tblRptFreeSpotList  (LastName, FirstName,
EmailAddr, ParkingLot, PreferLot, DH)" & _
       " SELECT TOP " & Num & " MasterList.LastName, MasterList.FirstName,
MasterList.EmailAddr, MasterList.ParkingLot, MasterList.PreferLot,
MasterList.DH FROM MasterList" & _
       " WHERE MasterList.PreferLot = " & "'" & Forms!frmMain!txtPreferLot
&
"'" & _
       " ORDER BY MasterList.DH"

DoCmd.RunSQL StrSQL

There may be other problems in the SQL statement.  I find it is best for me
to build the SQL statement in a variable and then Debug.print it to see if
it looks correct.  IF it does, I copy it into a new query and attempt to run
it.  If it runs, I comment out the debug.print strSQL statement and let code
run.