The OE settings addon stores basic network info (technology, interface, SSID, password, IP details) in an XML file which is read at startup by the networking init script. The script builds default.profile and this is used as the active 'profile' in connman-speak by connman when it's started. If the wireless NIC is active but not the default interface (in OE settings) default.profile will also record details of WLANs it can see. It's possible to edit the content while connman is running but each time connman goes to read the file it'll overwrite whatever you put in it. To change what ends up in default.profile you'll need to hack the init scripts that build it at startup, which is easiest done by building your own OpenELEC images. Once you've got a working build it's fairly simple to clear only the built package that contains the init scripts so that any change you made are picked up on the next build. If the system is only (re)building one small package each time the build only takes a couple of minutes.
I've no idea what support for WPA Enterprise is like but documentation for connman is in the sources. Make sure you grab v0.77 as this is what we're currently using. Be aware that connman did a major API rewrite in 0.78/79 and the latest build is 0.80. Sometime after OpenELEC 2.0 ships the devs need to re-implement connman to account for the changes so that we catch-up on their releases. This probably means the init scripts will change and require some rework to any hacking you do.
Adding Enterprise WPA support isn't high on the agenda for the project as our primary target audience is consumer users. It can probably be hacked to work and if it's really simple we might consider adding it as a capability to the main builds, but it's not guaranteed. If this were me (with a busy day-job) I'd start thinking about a long Ethernet cable or a cheap wireless bridge device as being significantly easier and more future-proof to live with. Just my $0.02.
If you go ahead, post Q's here. There are not too many people who understand how connman works (and I'm not really one of them) but we'll advise where we can if you ask the right questions!