Why would you want to add a new record to the value list table?
Do you mean that if you enter a value not already on the list, you want a record with the new value added to the value list table?
Option 1: Write a script performed by a script trigger that checks the value in the field and adds it if it is not already present in the value list table.
Option 2: Set up your value list to list its values from the same table as the one where you are entering this new value, then changes will appear automatically in the value list.
Note: Option 2 can look like a great idea, but it can make managing your value list--especially correcting misspellings and other data entry errors quite a bit of a hassle.
Option 2 should work just fine for what im doing. I have the Spots::Character1 field getting values from the Characters::Character field currently and it does populate the value list when i add a new name to the Characters::Character field but if i type a new name in the Spots::Character1 field it does not add a record in the Characters table.
Option 2 presumes that there is no characters table to update.