You cannot buy an accessory online unless you already have a mobile phone or SIM contract from EE. You are expected to pay for it along with your existing EE mobile plan. That's why it's telling you to login to upgrade your existing plan or add another device.
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To phone EE CS: Dial Freephone +44 800 079 8586 - Option 1 for Home Broadband & Home Phone or Option 2 for Mobile Phone & Mobile Broadband
ISPs: 1999: Freeserve 48K Dial-Up > 2005: Wanadoo 1 Meg BB > 2007: Orange 2 Meg BB > 2008: Orange 8 Meg LLU > 2010: Orange 16 Meg LLU > 2011: Orange 20 Meg WBC > 2014: EE 20 Meg WBC > 2020: EE 40 Meg FTTC > 2022:EE 80 Meg FTTC SoGEA > 2025 EE 150 Meg FTTP
