Assuming your field is a user/group field with multiple selections, the below code should get you started. I adapted the code found at http://gemsolution.blogspot.com/2009/04/fun-with-spfielduservaluecollection.html to your specs.
StringBuilder allEmails = new StringBuilder();
using (SPSite site = new SPSite("http://mysite.com/sitecollection"))
{
using (SPWeb web = site.OpenWeb("mysitename"))
{
SPList oList = web.Lists["ListName"];
SPListItemCollection oListItems = oList.Items;
foreach (SPListItem oListItem in oListItems)
{
//Gets a collection of all the User and Group objects from the UserGroup Field
SPFieldUserValueCollection oFieldUserValueCollection =
new SPFieldUserValueCollection(web, oListItem["FieldName"].ToString());
//Next, loop through the Values in the Collection
foreach (SPFieldUserValue oFieldUserValue in oFieldUserValueCollection)
{
//now we need to test if the SPFieldUserValue is a
//User or a Group, because if we simply assign a user
//we will get a Null Reference Exception if it is a Group
//It is a Group
if (oFieldUserValue.User == null)
{
//Create and assign a new SPGroup object by using the
//Lookup value to return a Group from the current Site(SPWeb)
SPGroup oGroup = web.Groups.GetByID(oFieldUserValue.LookupId);
}
//It is a User
else
{
//Create and assign a new SPUSer object by using the User
//property of the SPFieldUserValue object
SPUser oUser = oFieldUserValue.User;
allEmails.Append(oUser.Email + ",");
}
}
}
}
}
string allEmailsInAString = allEmails.ToString();