High-density polyethylene (HDPE) pipes are becoming increasingly popular, being used in various fields, such as construction, marine, petroleum, water transfer, process water, methane gas collection, oil and gas gathering, gas distribution systems, mining, acid and wet gas lines, offshore oil and gas and in nuclear power plants. Higher-order guided Lamb wave (UGW) modes can be used to detect various defects in complex structures. We will apply this methodology to one of the types of plastic—the structure of high-density polyethylene (HDPE). However, the excitation of UGW modes faces numerous challenges, especially when there is a need to identify which mode is excited. It is essential to note that, in the higher frequency range, multiple different higher-order modes can usually be excited. This can make it difficult to determine which modes have actually been excited. The objective of this research was to successfully excite and receive various higher-order UGW modes in high-density polyethylene structures using both ultrasonic single-element transducers and a phased array. Theoretical calculations were performed using a variety of methods: semi-analytical finite element (SAFE) method, 2D spatial–temporal spectrum analysis and finite element modeling (FEM). The results obtained from both measurements and simulations clearly demonstrate the possibility of efficiently exciting and receiving different Lamb wave modes possessing different phase velocities.