An access point is defined by its ssid. If you want to have more than one ssid then you have to create additional access points, one for each ssid. The built-in WiFi device of a Raspberry Pi can only spawn one access point. You can verify it with:
rpi ~$ iw phy0 info
--- snip ---
valid interface combinations:
* #{ managed } <= 1, #{ P2P-device } <= 1, #{ P2P-client, P2P-GO } <= 1,
total <= 3, #channels <= 2
* #{ managed } <= 1, #{ AP } <= 1, #{ P2P-client } <= 1, #{ P2P-device } <= 1,
total <= 4, #channels <= 1
Here you find in the second combination #{ AP } <= 1
, that means: number of access points less or equal one. So you have to add an USB/WiFi dongle for each additional ssid. Because you used systemd-networkd following the setup Access point as WiFi router/repeater, optional with a bridge it is not a big issue to add an access point. Just plug in a compatible USB/WiFi dongle and you will find an interface wlan1. Using the example in the setup then configure it.
To setup wpa_supplicant for the additional access point using wlan1 create these files with your settings:
rpi ~$ sudo -Es
rpi ~# cat > /etc/wpa_supplicant/wpa_supplicant-wlan1.conf <<EOF
country=DE
ctrl_interface=DIR=/var/run/wpa_supplicant GROUP=netdev
update_config=1
network={
ssid="RPiNet2"
mode=2
frequency=2412
key_mgmt=WPA-PSK
proto=RSN WPA
psk="verySecretPassword"
}
EOF
rpi ~# chmod 600 /etc/wpa_supplicant/wpa_supplicant-wlan1.conf
rpi ~# systemctl disable wpa_supplicant.service
rpi ~# systemctl enable [email protected]
rpi ~# cat > 16-wlan1.network <<EOF
[Match]
Name=wlan1
[Network]
Address=192.168.5.1/24
DHCPServer=yes
[DHCPServer]
DNS=84.200.69.80 1.1.1.1
EOF
rpi ~# systemctl start [email protected]
rpi ~# systemctl daemon-reload
rpi ~# systemctl restart systemd-networkd.service
Now you should find a second ssid RPiNet2 on the air.