An access point allows nearby WiFi devices to connect to its wireless network, while a station can connect to an existing hotspot or router's WiFi network. The document discusses how to configure an ESP8266 chip as either an access point or station using Arduino code. It provides examples of common WiFi library commands to connect to networks, check connection status, and get the IP address. Creating a softAP turns the ESP8266 into its own access point, while the WiFiClient class allows connecting to internet servers.