Hi Divesh,
From what you are seeing with the network, it could be that there is some conditional access setup for accessing Teams. I assume they are using ADFS as their authentication method also.
Without looking at the logs it is hard to tell what the exact issue is.
The SmartHub 500 should work with an on-prem exchange as these use two different engines to get the information, Exchange web services for the callendaring via autodiscover.<domain> and the connection to Microsoft Teams itself.
You can use on-prem Exchange as long as the SMTP and UPN's are the same otherwise you will start to see issues. Also you must be using a supported version of Exchange, 2013 SP1 and above from my last look at the specifications, using Exchange 2010 is definitely not supported.
An E5 license will work on the devices, you will need to create the accounts as you would a room and not a normal user and assign the license in the usual way. Technically it is a bit of an overkill for the device as it won't use the extended range of features an E5 offers.
As long as the room system application is being updated (currently 4.0.64.0) you can change the theming inside the setup itself. You can also change the mode of the application within there also.
The microphone pickup on these devices are pretty good, especially for huddle rooms. The 2 far field microphones are built into the top of the display.
You can if the room size or layout requires add external microphones to the solution if needed.
I hope that helps.
Thanks,
Dan