You can add custom field for Customer by following this link https://magento.stackexchange.com/questions/5905/adding-custom-attribute-to-customer-registration-form or the tutorial http://www.magentocommerce.com/wiki/5_-_modules_and_development/customers_and_accounts/registration_fields
Then add validation condition for your attribute just like other validations in Customer Model file app/code/core/Mage/Customer/Mode/Customer.php. Arround line number 792 look for method public function validate()