There are a number of issues in trying to send mail for various accounts through a home SMTP server.
First, if you read the doccumentation on "virtual domains" for your mailserver, it will tell you how to allow outbound mail to appear to come from some other address than mailserver.homenetwork.net or whatever. This is pretty common, most mailservers have hostnames other than the unqualified domain name that mail appears to be from (homenetwork.net in this case).
Next, you need to deal with the fact that a lot of mail servers are configured to reject connections from servers at IP addresses that are listed as part of the IP pool of an ISP. This is a very crude method of spam blocking, but more and more administrators include it by default in their configurations.
To get around this, you'll have to relay mail for those hosts through your ISP's mailserver. This may be possible on a per-domain basis, your mailer may allow you to fall back to this route if delivery fails, or you may end up routing everything through the ISP's server.
Most ISP's are pretty good about this, but some will object to sending mail that appears to come from somenetwork.com through their ispnetwork.com host. This would allow people to relay mail from illegitimate networks through thier valid network and open them to spam relays if they weren't careful. If you have the bad luck to end up in this situation, and can only send mail that originates from ispnetwork.com, look for another ISP.
My general advice is try it, and if it doesn't work find a way around it.