Here's how you'd do it via code (note: solution does not provide error checking)
using (SPSite siteColl = new SPSite("http://yourSPSite"))
{
using (SPWeb site = siteColl.OpenWeb())
{
SPList customList = site.Lists.TryGetList("Your List Name");
SPFieldCollection fieldColl = customList.Fields;
SPFieldUser userField = (SPFieldUser)fieldColl.GetField("ColumnName");
userField.AllowMultipleValues = true;
userField.Update();
}
}
And a slightly shorted version:
using (SPSite siteColl = new SPSite("http://yourSPSite"))
{
using (SPWeb site = siteColl.OpenWeb())
{
SPList customList = site.Lists.TryGetList("Your List Name");
SPFieldUser userField = (SPFieldUser)customList.Fields["ColumnName"];
userField.AllowMultipleValues = true;
userField.Update();
}
}