Yes, you can use 1:N Peripheral-Central mode through BLESS, where N is up to 4 since BLESS supports up to four simultaneous connections. If the peripheral device is already connected, you can start advertising again for a new connection. Within 4 simultaneous connection, you can implement any combination of central and slave roles.
PSoC 6 BLE supports upto 4 simultaneous connection in any valid combination of Master and slave, say as a Master to one peer device and as slaves to three peer devices or as slave to 4 peer devices.
You can refer to the Multi-Slave Multi-Master examples from the following links:
Let me know if you have any further queries about the Multi-Slave Multi-Master examples.