Just make it point to the PRIMARY KEY of the referenced table:
PO_Table (POId PRIMARY KEY, MainPharmacyID, SupplierID, PreparedBy)
PO_Items_Table (POItemID, POId FOREIGN KEY REFERENCES PO_Table (POId), ...)
Actually, in your PO_Table I don't see any other candidate key except POId, so as for now this seems to be the only available solution to me.
What are the "two options" you are considering?
Update:
Putting POItemID in the PO_Table is not an option unless you want your orders to have no more than one item in them.
Just look into it: if you have but a single column which stores the id of the ordered item in the order table, where are you going to store the other items?
Update 2:
If there is a one-to-one relationship, normally you just merge the tables: combine all fields from both tables into a single record.
However, there are cases when you need to split the tables. Say, one of the entities is rarely defined but has too many fields.
In this case, you make a separate relation for the second entity and make its PRIMARY KEY column also a FOREIGN KEY.
Let's imagine a model which describes the locks and the keys, and the keys cannot be duplicated (so one lock matches at most one key and vice versa):
Pairs (PairID PRIMARY KEY, LockID UNIQUE, LockProductionDate, KeyId UNIQUE, KeyProductionDate)
If there is no key for a lock or no lock for a key, we just put NULLS into the corresponding fields.
However, if all keys have a lock but only few locks have keys, we can split the table:
Locks (LockID PRIMARY KEY, LockProductionDate, KeyID UNIQUE)
Keys (KeyID PRIMARY KEY, KeyProductionDate, FOREIGN KEY (KeyID) REFERENCES Locks (KeyID))
As you can see, the KeyID is both a PRIMARY KEY and a FOREIGN KEY in the Keys table.
You may want read this article in my blog:
, which describes some ways to map ER model (entities and relationship) into the relational model (tables and foreign keys)