Unfortunately it is not possible at least with YAML implementation. BLE Client requires MAC address when created and there can be max 3 of them, as mentioned in BLE Client — ESPHome
It is not possible to disconnect and connect to another device with same BLE Client.
I believe it supports multiple thermostats at the same time as it is PC based solution and doesn’t have limited hardware like ESP32. It will require that all devices are in range of PC’s Bluetooth dongle.