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Major isp advantage
Big wallets of the largest providers can make a difference. As capacity increases the large isp's can continue to add more server or computing power to handle the loads as well as access numbers. However many small internet providers who purely provide access work as hard and with the quality providers I have not seen any noticeable difference in quality of connections with the major provider versus the small provider. Your location and line quality will have a greater impact than a major versus minor provider. Each provider is its own unique service and therefore quality the same.
Customer support
Can come in a variety of means including email, live online text chat, online help guides and telephone. Like many big business's though the telephone can sometimes get backlogged in a hurry. Some small internet providers or low cost intenet providers may charge for customer support by phone however many users never call their isp. The rates if there is a fee should be listed in their frequently asked questions.
Email
One of the greates differences is in the email quality. The email reliability is likely the same for most but the interface for the major internet providers is typically of higher quality as are the filtering, spam, inbox and options. Again however using a free email service or a fee based email (usually $10 to $30 annually.) can again change this around. Your included ISP email box from major ISP's or fee based may offer more storage space per email account as well as more extras like MSN is offering a virtual online calendar, programmable email alerts, link your email and chat accounts, etc. Some services are free some are fee based.
Note: Internet--Access uses and test both Major ISP and Small ISP providers alike