Ah, right. Leading zero.
Well, you have to ask yourself what this dialing code represents, and how you are holding this. My guess is that you think it's a number, so the field you have defined is a number field. As others have said, it is possible to format a number to show one or more leading zeros, but the number will remain stored as just the number. Thus you enter 01457, this stores as 1457, but you can show it as 01457.
However, further thought will reveal that this code is not a number at all, but a code (see the answer is in the question!). So you will never have to use it as a number. So why store it as a number? Store it as text. Then you can default in the leading zero.
That still leaves you with a minor problem. If you use a field with a default value in a form, when you move to the control with this value in it, it is highlighted. When the user types in the value, the leading zero you have so thoughtfully supplied gets over written! You will have to use a bit of code to move the insert point after the zero. I don't know how to do this offhand.
You said:
I could create a new table as a look up table as such and store an ID associated with the code although again not the initial idea that I had.
Why would you want to store an ID? All I meant was to have a single field table holding a list of valid codes. Create your control for the code on your input form and attach a list box derived from your table. Since all your values would have a leading zero, this would force correct entry. I accept that this may not be what you want to do.